TW202102547A - Photocurable composition, method for producing uneven structure, method for forming fine uneven pattern and uneven structure - Google Patents

Abstract

A photocurable composition for forming a resin layer of an uneven structure, the uneven structure including: a substrate; and a resin layer which is provided on the substrate and has fine unevenness formed on the surface. A cured film of the photocurable composition has a surface free energy of 15 mJ/m² to 40 mJ/m² measured based on the Kitazaki-Hata theory, and a hardness of 0.05 GPa to 0.5 GPa measured using a nanoindenter.

Description

Photocurable composition, method for manufacturing uneven structure, method for forming fine uneven pattern, and uneven structure

The present invention relates to a photocurable composition, a method for manufacturing a concave-convex structure, a method for forming a fine concave-convex pattern, and a concave-convex structure.

As a method of forming a fine uneven pattern on the surface of a substrate, a photolithography method or a nanoimprint method is known. The device of the photolithography method is expensive and the manufacturing process is complicated. In contrast to this, the nanoimprint method has the advantage of being able to produce fine concavo-convex patterns on the surface of the substrate with a simple device and process. In addition, the nanoimprint method can be regarded as a preferable method for forming a relatively wide and deep concave-convex structure, or various shapes such as a dome, a quadrangular pyramid, and a triangular pyramid.

Generally, in the industrial nanoimprint method, first, an expensive mother mold is produced in which the fine uneven structure on the surface is formed by the photolithography method or the electron beam drawing method. Then, an inexpensive replica mold in which the concave-convex structure of the master mold is replicated with an organic material is manufactured. After copying the mold to process the processed substrate for a certain number of repetitive use in consideration of productivity, the task is completed. In the industry, the duplication mold requires a function that can withstand repeated use. It helps reduce costs by increasing the number of repeated uses.

As a specific process of the nanoimprint method, the following ultraviolet (Ultraviolet, UV) method is widely used: the photocurable composition is contacted with the uneven surface of the mold, and cured by light (UV) irradiation, and then peeled off. Step UV method. The UV method is different from the heating, melting and crimping method, and has the advantages of not requiring large-scale heating, crimping equipment, or easy combination of roll to roll (roll to roll) and other continuous methods.

In response to adaptation as a replication model, a material with relatively good repeatability is disclosed (for example, Patent Document 1). According to this document, a composition containing acrylate, silicone macromonomers and initiators is heated and polymerized, the resulting resin composition is brought into contact with the concave and convex surface of the master mold, and the heat is melted and pressure-bonded. To make a copy model. Moreover, in the UV-type nanoimprint with a photocurable compound, a relatively good repeatability of about 20 times was achieved. However, the material described in Patent Document 1 needs to be heated, melted, and pressure-bonded when making a replica mold. That is, even in the formation of a concave-convex structure with a pattern area of several centimeters square, in order to fill the concave-convex structure of the mold with resin, it is necessary to apply a pressure of up to 20 MPa using a device equipped with a heating mechanism. Therefore, from the viewpoint of the manufacturing method of the replica mold, the adaptation to the industrial process is very limited.

In addition, as a material that can be adapted to the nanoimprint of the UV method, Patent Document 2 is a material that has excellent coating properties, rapid curing properties, and film curability, and excellent shape transferability in the nanoimprint method. , Reveals a specific cationic hardening material. Patent Document 2 discloses that it can be used 50 times with regard to the repeatability of transfer. However, Patent Document 2 relates to an imprint with a pattern shape of 1 to 2 microns in size. There is no record related to pattern formation at the nano-size level. Furthermore, in any of the disclosure examples, regarding the adaptation of the copy mold, there is no description of the adaptation of using the same material for making the copy mold to repeatedly use the copy mold that was originally made. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2012/018043 [Patent Document 2] Japanese Patent Laid-Open No. 2018-141028

[The problem to be solved by the invention]

Regarding the findings of the inventors, in adapting to the industrial manufacturing method of the nanoimprint method, from the viewpoint of the overall process including the manufacturing steps of the replica mold and the degree of freedom of the shape (size) of the substrate to be processed, The existing technology does not satisfy all. In particular, there is still room for improvement in the photocurable composition used in the formation of resin molds for nanoimprint typified by replica molds.

The present invention was made in view of the aforementioned circumstances. Specifically, the object of the present invention is to provide a photocurable composition for forming a resin mold that can be used repeatedly in adaptation as a replication mold. [Means to solve the problem]

The present invention is as follows.

通式（1）中， R₁ 相同或不同地表示選自由氫原子、氟原子、鹵素原子、碳數1～20的烴基、碳數6～20的芳基、碳數6～20的芳烷基、碳數1～20的聚醚基及碳數1～20的氟碳基所組成的群組中的任一原子或基， L₁ 的至少一個含有選自由環氧基、羥基、胺基、乙烯基醚基、內酯基、丙烯基醚基、烯烴基、氧雜環丁基、乙烯基、丙烯酸酯基、甲醇基及羧基所組成的群組中的光反應性官能基，於L₁ 並非光反應性官能基的情況下，相同或不同地表示選自所述R₁ 中的原子或基， n及1-n表示各單元的比率。 [化2]

通式（2）中， L₂ 為選自由環氧基、胺基、乙烯基醚基、內酯基、丙烯基醚基、醇基、烯烴基、氧雜環丁基、乙烯基、丙烯酸酯基、甲醇基及羧基所組成的群組中的光反應性官能基， R₂ ～R₅ 中的至少一個為選自由氟、含有氟的碳數1～10的烷基、含有氟的碳數1～10的烷氧基及含有氟的碳數2～10的烷氧基烷基所組成的群組中的含氟的基， 於R₂ ～R₅ 並非含氟的基的情況下，R₂ ～R₅ 為選自由氫、碳數1～10的烷基、碳數1～10的烷氧基及碳數2～10的烷氧基烷基所組成的群組中的有機基， R₂ ～R₅ 可相同亦可不同，另外，R₂ ～R₅ 可相互鍵結而形成環結構， 虛線表示該部分的鍵可為碳-碳單鍵亦可為碳-碳雙鍵。 4. 如1.至3.中任一項所述的光硬化性組成物，其包含光硬化起始劑。 5. 如2.或3.所述的光硬化性組成物，其中， 所述光硬化性單體包含具有能夠進行陽離子聚合的開環聚合性基的化合物。 6. 一種凹凸結構體的製造方法，其是使用如1.至5.中任一項所述的光硬化性組成物來製造凹凸結構體，所述凹凸結構體包括：基板；以及樹脂層，設置於該基板上且表面形成有微細凹凸，並且所述製造方法包括壓接步驟， 所述壓接步驟是將具有微細凹凸圖案的模具壓接於藉由所述光硬化性組成物而設置於基板上的光硬化性層，藉此於所述樹脂層的表面形成與所述微細凹凸圖案對應的微細凹凸圖案。 7. 如6.所述的凹凸結構體的製造方法，其更包括： 光照射步驟，於所述壓接步驟之後，於壓接所述模具的狀態下照射光，藉此使所述光硬化性層硬化而製成硬化層；以及 剝離步驟，自所述硬化層剝離所述模具。 8. 一種形成微細凹凸圖案的方法，其是重覆使用包括如下樹脂層的基板來形成微細凹凸圖案，所述樹脂層是由如1.至5.中任一項所述的光硬化性組成物形成且表面形成有微細凹凸。 9. 一種凹凸結構體，包括： 基板；以及 樹脂層，設置於該基板上，且由如1.至4.中任一項所述的光硬化性組成物形成，並且表面形成有微細凹凸。 [發明的效果]1. A photocurable composition for forming the resin layer of a concavo-convex structure including a substrate and a resin layer, the resin layer is provided on the substrate with fine concavities and convexities formed on the surface, and the photocurable composition Among them, the surface free energy measured by the following evaluation method 1 is 15 mJ/m ² to 40 mJ/m ² , and the hardness measured by the following evaluation method 2 is 0.05 GPa to 0.5 GPa. (Evaluation method 1) First, a photocurable composition is applied to a substrate to form a photocurable film, and ultraviolet rays are irradiated to obtain a cured cured film. Next, a contact angle meter was used to measure the contact angles of water, diiodomethane, and 1-bromonaphthalene with respect to the cured film. Then, calculate the surface free energy according to Kitazaki-Hata's theory. (Evaluation method 2) First, a cured film was obtained by the same method as the above-mentioned evaluation method 1. Next, a nanoindentor is used to press a Berkovich indenter against the hardened film, and the hardness is calculated based on the value of the detected stress. 2. The photocurable composition according to 1., wherein the photocurable composition contains (a) a photocurable monomer, or a photocurable monomer and a binder resin, and (b) has photoreactivity Functional group additives, with respect to the total amount of (a) photocurable monomers, or photocurable monomers and binder resins, and (b) additives with photoreactive functional groups, (b) have photoreactive functions The content rate of the base additive is 0.001% by mass to 10% by mass. 3. The photocurable composition according to 2., wherein the (b) additive having a photoreactive functional group includes an additive represented by the following general formula (1) and/or contains the following general formula (2) ) Additives of the structure indicated. [化1]

In the general formula (1), R _{1 is the} same or different and represents selected from a hydrogen atom, a fluorine atom, a halogen atom, a hydrocarbon group having 1 to 20 carbons, an aryl group having 6 to 20 carbons, and an alkane having 6 to 20 carbons. Group, any atom or group in the group consisting of a polyether group with 1 to 20 carbons and a fluorocarbon group with 1 to 20 carbons _{, at least one of L 1} contains an epoxy group, a hydroxyl group, and an amino group , Vinyl ether group, lactone group, propenyl ether group, alkene group, oxetanyl group, vinyl group, acrylate group, methanol group and carboxyl group consisting of photoreactive functional group, in L ₁ is not the case where the photoreactive functional group, the same or different, represent R ₁ is selected from the atom or group, n and 1-n represents the ratio of the respective units. [化2]

In the general formula (2), L ₂ is selected from epoxy groups, amino groups, vinyl ether groups, lactone groups, propenyl ether groups, alcohol groups, alkene groups, oxetanyl groups, vinyl groups, and acrylate groups. At least one of R ₂ to R ₅ is selected from the group consisting of fluorine, fluorine-containing alkyl group having 1 to 10 carbon atoms, and fluorine-containing carbon number A fluorine-containing group in the group consisting of 1-10 alkoxy groups and fluorine-containing alkoxyalkyl groups having 2-10 carbon atoms. When R ₂ to R _{5 are} not fluorine-containing groups, R ₂ to R ₅ are organic groups selected from the group consisting of hydrogen, alkyl groups having 1 to 10 carbons, alkoxy groups having 1 to 10 carbons, and alkoxyalkyl groups having 2 to 10 carbons, R ₂ to R ₅ may be the same or different. In addition, R ₂ to R ₅ may be bonded to each other to form a ring structure. The dotted line indicates that the bond in this part may be a carbon-carbon single bond or a carbon-carbon double bond. 4. The photocurable composition according to any one of 1. to 3. which contains a photocuring initiator. 5. The photocurable composition according to 2. or 3., wherein the photocurable monomer contains a compound having a ring-opening polymerizable group capable of undergoing cationic polymerization. 6. A method for manufacturing a concavo-convex structure, which uses the photocurable composition as described in any one of 1. to 5. to produce a concavo-convex structure, the concavo-convex structure comprising: a substrate; and a resin layer, Is provided on the substrate with fine concavities and convexities formed on the surface, and the manufacturing method includes a crimping step, wherein the crimping step is to crimp a mold having a fine concavo-convex pattern to the photocurable composition. The photocurable layer on the substrate thereby forms a fine concavo-convex pattern corresponding to the fine concavo-convex pattern on the surface of the resin layer. 7. The manufacturing method of the concavo-convex structure as described in 6., further comprising: a light irradiation step, after the crimping step, irradiating light in a state where the mold is crimped, thereby hardening the light The sexual layer is cured to form a hardened layer; and the peeling step is to peel off the mold from the hardened layer. 8. A method for forming a fine concavo-convex pattern, which is to repeatedly use a substrate comprising a resin layer to form the fine concavo-convex pattern, the resin layer being composed of the photocurable composition as described in any one of 1. to 5. The surface is formed with fine concavities and convexities. 9. A concavo-convex structure, comprising: a substrate; and a resin layer provided on the substrate and formed of the photocurable composition as described in any one of 1. to 4. with fine concavities and convexities formed on the surface. [Effects of the invention]

By using the photocurable composition of the present invention, a concavo-convex structure that can be used repeatedly in adaptation as a replica mold can be obtained.

Hereinafter, an embodiment of the present invention will be described. The description of "A to B" related to the numerical range means more than A and less than B unless otherwise specified. For example, the description of "1% to 5%" means 1% or more and 5% or less. In this specification, the photocurable composition of the present invention may be expressed as the "first photocurable composition". In addition, the following photocurable composition is sometimes expressed as a "second photocurable composition": the first photocurable composition is used to form a substrate having a resin layer with a fine uneven structure formed on the surface thereof into a replica mold , Use the copy mold to process the photocurable composition used when processing the substrate to be processed. Regarding the expression of the group (atomic group) in this specification, the expression that does not describe substituted or unsubstituted includes both an unsubstituted group and a substituted group. For example, the term "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group).

＜Light-curable composition＞ The photocurable composition of this embodiment is used to form a resin layer in a concavo-convex structure, the concavo-convex structure comprising: a substrate; and a resin layer provided on the substrate and having fine concavities and convexities formed on the surface. The photocurable composition of the present embodiment preferably contains (a) a photocurable monomer or a photocurable monomer and a binder resin, and (b) an additive having a photoreactive functional group. Moreover, it is preferable that the content rate of the additive which has a photoreactive functional group of (b) with respect to the total amount of (a) and (b) is 0.001 mass%-10 mass %. Hereinafter, each component that can constitute the photocurable composition will be described. Just in case, the photocurable composition of the present embodiment preferably contains the components described below, but it is only required that the characteristic values measured by (evaluation method 1) and (evaluation method 2) described later are specified Within the range of, the components described below may not be included.

(Photocurable monomer) As the photocurable monomer, a compound having a reactive double bond group, a ring-opening polymerizable compound capable of undergoing cationic polymerization, and the like can be cited. Particularly preferred is a ring-opening polymerizable compound (specifically, a compound containing a ring-opening polymerizable group such as epoxy group or oxetanyl group) that has small curing shrinkage and good dimensional reproducibility of uneven shapes and can undergo cationic polymerization. .

The photocurable monomer may have one reactive group in one molecule, or may have a plurality of them. It is preferable to use a compound having two or more reactive groups in one molecule. The upper limit of the number of reactive groups in one molecule does not particularly exist, and for example, it is two, preferably four. As the photocurable monomer, only one type may be used, or two or more types may be used. When two or more types are used, compounds with different numbers of reactive groups can be mixed and used in any ratio. In addition, a compound having a reactive double bond group and a ring-opening polymerizable compound capable of cation polymerization may be mixed and used in an arbitrary ratio. In addition, by appropriately selecting the type or composition ratio of the photocurable monomer, a three-dimensional network structure can be efficiently formed on the inside and the surface after curing by light irradiation. Thereby, the resin hardness mentioned later can be maintained in an appropriate range.

As a specific example when the photocurable monomer is a compound having a reactive double bond group, for example, the following can be cited. Fluorodiene (CF ₂ =CFOCF ₂ CF ₂ CF=CF ₂ , CF ₂ =CFOCF ₂ CF(CF ₃ )CF=CF ₂ , CF ₂ =CFCF ₂ C(OH)(CF ₃ )CH ₂ CH=CH ₂ , CF ₂ =CFCF ₂ C(OH)(CF ₃ )CH=CH ₂ , CF ₂ =CFCF ₂ C(CF ₃ )(OCH ₂ OCH ₃ )CH ₂ CH=CH ₂ , CF ₂ =CFCH ₂ C(C (CF ₃ ) ₂ OH)(CF ₃ )CH ₂ CH=CH ₂ etc.) and other olefins. Cyclic olefins such as norbornene and norbornadiene. Alkyl vinyl ethers such as cyclohexyl methyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, and ethyl vinyl ether. Vinyl esters such as vinyl acetate. (Meth) acrylic acid, phenoxyethyl acrylate, benzyl acrylate, stearyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, allyl acrylate, 1,3-butanediol diacrylate , 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, ethoxyethyl acrylate, Methoxyethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyoxyethylene glycol diacrylate, tripropylene glycol diacrylate, acrylic acid 2-hydroxyethyl, 2-hydroxypropyl acrylate, 4-hydroxybutyl vinyl ether, -N,N-diethylaminoethyl acrylate, -N,N-dimethylaminoethyl acrylate Esters, N-vinylpyrrolidone, dimethylaminoethyl methacrylate, methyl methacrylate, trifluoroethyl methacrylate, benzyl methacrylate, etc. (meth)acrylic acid and its derivatives , Or these fluorine-containing acrylates, polyfunctional acrylates, etc.

Among the photocurable monomers, examples of the ring-opening polymerizable compound capable of undergoing cationic polymerization include the following. In terms of long-term storage stability and suppression of deterioration in the dimensional accuracy of the uneven structure due to hardening shrinkage, etc., the compound is preferred.

1,7-butadiene diepoxide, 1,2-epoxydecane, 1,2-epoxydodecane, 2-ethylhexyl glycidyl ether, cyclohexene epoxide, α -Pinene oxide, dicyclopentadiene oxide, limonene monooxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3', 4'-Epoxycyclohexane carboxylate, bis(3,4-epoxycyclohexyl)adipic acid, (3,4-epoxycyclohexyl)methanol, 1,2-epoxy- 4-vinylcyclohexane, (3,4-epoxy-6-methylcyclohexyl) methyl-3,4-epoxy-6-methylcyclohexane carboxylate, ethylene1,2 -Bis(3,4-epoxycyclohexanecarboxylic acid) ester, methacrylic acid [(3,4-epoxycyclohexane)-1-yl]methyl, (3,4-epoxy) Cyclohexyl) ethyl trimethoxysilane, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, dicyclohexyl-3,3'-diepoxide, bisphenol A epoxy resin, halogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxidized polybutadiene, o-cresol novolak type epoxy resin, m-cresol novolak type epoxy resin, p-cresol novolak type epoxy resin , Phenol novolac type epoxy resin, polyglycidyl ether of polyol, 1,2-epoxy-4-(2-oxane) of 2,2-bis(hydroxymethyl)-1-butanol Base) cyclohexane adduct, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate and ε-caprolactone adduct, adipic acid Bis(3,4-epoxycyclohexane-1-ylmethyl) ester, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexene carboxylate Epoxy compounds such as alicyclic epoxy resins or epoxy compounds such as glycidyl ethers and glycidyl esters of hydrogenated bisphenol A. 3-methyl-3-(butoxymethyl)oxetane, 3-methyl-3-(pentyloxymethyl)oxetane as a compound with one oxetanyl group , 3-methyl-3-(hexyloxymethyl)oxetane, 3-methyl-3-(2-ethylhexyloxymethyl)oxetane, 3-methyl- 3-(octyloxymethyl)oxetane, 3-methyl-3-(decanoyloxymethyl)oxetane, 3-methyl-3-(dodecanoyloxy) Methyl)oxetane, 3-methyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(butoxymethyl)oxetane, 3 -Ethyl-3-(pentyloxymethyl)oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(2-ethyl Hexyloxymethyl)oxetane, 3-ethyl-3-(octyloxymethyl)oxetane, 3-ethyl-3-(decyloxymethyl)oxetane Cyclobutane, 3-ethyl-3-(dodecyloxymethyl)oxetane, 3-(cyclohexyloxymethyl)oxetane, 3-methyl-3- (Cyclohexyloxymethyl)oxetane, 3-ethyl-3-(cyclohexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxy Etidine, 3,3-dimethyloxetane, 3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, 3-ethyl- 3-hydroxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, 3-n-propyl-3-hydroxymethyloxetane, 3-isopropyl 3-hydroxymethyloxetane, 3-n-butyl-3-hydroxymethyloxetane, 3-isobutyl-3-hydroxymethyloxetane, 3-th Dibutyl-3-hydroxymethyloxetane, 3-tert-butyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyl)oxetane Butane, 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxetane, etc., bis(3-ethyl) as a compound having two or more oxetanyl groups -3-oxetanylmethyl) ether, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)]ethane, 1,3-bis[(3-ethyl-3- Oxetanylmethoxy)]propane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)]-2,2-dimethyl-propane, 1,4-bis(3 -Ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, 1,4-bis[(3-methyl -3-oxetanyl)methoxy]benzene, 1,3-bis[(3-methyl-3-oxetanyl)methoxy]benzene, 1,4-bis{[(3 -Methyl-3-oxetanyl)methoxy]methyl}benzene, 1,4-bis{[(3-methyl-3-oxetanyl)methoxy]methyl} ring Hexane, 4,4'-bis{[(3-methyl-3-oxetanyl)methoxy]methyl}biphenyl, 4,4'-bis{[(3-methyl-3 -Oxetanyl)methoxy)methyl)bis Cyclohexane, 2,3-bis[(3-methyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane, 2,5-bis[(3-methyl-3 -Oxetanyl)methoxy]bicyclo[2.2.1]heptane, 2,6-bis[(3-methyl-3-oxetanyl)methoxy]bicyclo[2.2.1] Heptane, 1,4-bis[(3-ethyl-3-oxetanyl)methoxy]benzene, 1,3-bis[(3-ethyl-3-oxetanyl)methan Oxy]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 1,4-bis{[(3-ethyl-3- Oxetanyl)methoxy]methyl}cyclohexane, 4,4'-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}biphenyl, 4 ,4'-Bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}bicyclohexane, 2,3-bis[(3-ethyl-3-oxetan Yl)methoxy]bicyclo[2.2.1]heptane, 2,5-bis[(3-ethyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane, 2, Oxetane compounds such as 6-bis[(3-ethyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane and xylylene dioxetane. Lactone compounds. Allyl ether compounds, etc.

On the basis of the entire photocurable composition (100% by mass), the content of the photocurable monomer in the photocurable composition is preferably 10% by mass to 99.5% by mass, more preferably 20% by mass to 99.5% by mass. % By mass, more preferably 30% by mass to 99.5% by mass. In addition, when the binder resin described later is included, it is preferably 50% by mass to 99.5% by mass, more preferably 60% by mass to 99.5% by mass, and still more preferably 70% by mass to 99.5% by mass. In either case, the photocurable monomer may be used alone, or two or more of them may be mixed and used. By adjusting the content of the photocurable monomer to the above range, a three-dimensional network structure can be effectively formed on the surface and/or inside of the cured resin layer. Moreover, it is easy to adjust the resin hardness mentioned later to an appropriate range.

(Adhesive resin) The binder resin refers to, for example, a polymer obtained by polymerizing the photocurable monomer in advance or a polymer polymerized by other methods. From the viewpoints of compatibility with curable monomers and physical properties of the film after curing, the binder resin is preferably, for example, a polymer prepared by prepolymerizing the photocurable monomer or an amorphous resin. Cyclic olefin polymer. In addition, as preferred binder resins, polyacrylic resins, polyether resins, polyoxetanyl resins, polyester resins, cyclic olefin polymers, and the like can also be cited. As an example of the cyclic olefin polymer, a fluorine-containing cyclic olefin polymer represented by the general formula (1) of Japanese Patent No. 5466705 can be cited. This fluorine-containing cyclic olefin polymer is different from general fluororesins in that it has a moderate dipole moment due to the characteristics of the arrangement of fluorine atoms and fluorine-containing substituents. Therefore, while having characteristics as a fluororesin, there is a tendency that it has good affinity with general-purpose organic solvents or other components in the photocurable composition. Therefore, it has the following advantages: uniform dissolution during the preparation of the composition; good compatibility even in the form hardened by light irradiation; no whitening and the like are caused, and a uniform and transparent hardened resin layer and the like can be obtained.

In the case of using a binder resin, the amount of the binder resin is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass based on the entire photocurable composition (100% by mass) ~40% by mass, more preferably 1% by mass to 30% by mass. In the case of using a binder resin, it can be used alone or in combination of two or more. By adjusting the content of the binder resin within the above range, the viscosity of the photocurable composition can be adjusted. For example, the viscosity can be increased to suppress sag during coating, or to improve uniformity problems caused by fluctuations in the coating surface.

From the standpoint of compatibility with other components in the photocurable composition, the weight average molecular weight of the binder resin is preferably calculated as a value measured by gel permeation chromatography (Gel Permeation Chromatography, GPC) of a polystyrene standard 500 to 100,000, more preferably 500 to 80,000, still more preferably 500 to 50,000. By adjusting the weight average molecular weight of the binder resin to this range, compatibility with other components in the photocurable composition is good, and it is easy to obtain a photocurable composition that can be stored stably for a long period of time.

(Additives with photoreactive functional groups) The additive having a photoreactive functional group is preferably present on the surface of the film when the photocurable composition of the present embodiment is formed into a film. Thereby, the surface free energy of the cured film surface mentioned later can be adjusted.

The additive having a photoreactive functional group is preferably a compound that can be combined with the photocurable monomer due to the presence of the photoreactive functional group. Thereby, in the repeated use of the copy mold, a part of the copy mold can be prevented from migrating to the second photocurable composition used in the processing of the substrate to be processed, and the surface properties of the copy mold can be easily maintained in good condition. That is, the reusability of the copy mold can be improved. In addition, the additive having a photoreactive functional group is preferably present on the surface when the resin layer is formed. According to the findings of the present inventors, for example, the siloxane compound described later or the fluoropolymer having a specific cyclic structure is effectively biased in the vicinity of the film surface due to the presence of silicon atoms or fluorine atoms. Thereby, the surface free energy or hardness of the film surface can be controlled. Furthermore, it is considered that the reusability of the replica mold is improved.

Examples of the additive having a photoreactive functional group include a compound having a reactive double bond group as a photoreactive functional group, a compound having a ring-opening polymerizable group capable of cation polymerization as a photoreactive functional group, and the like. It is preferably a ring-opening polymerizable compound capable of undergoing cationic polymerization (specifically, a ring-opening polymerizable group such as an epoxy group, an oxetanyl group, an amino group, a vinyl ether group, an alcohol group, etc. A compound in which a cyclic polymerizable group is directly bonded) is preferred.

The additive having a photoreactive functional group may have one photoreactive group in one molecule, or may have a plurality of them. The additive having a photoreactive functional group preferably has two or more photoreactive groups in one molecule. The upper limit of the number of reactive groups in one molecule does not particularly exist, and for example, it is two, preferably four.

Regarding the additive having a photoreactive functional group, only one type may be used, or two or more types may be used. When two or more types are used, compounds with different numbers of reactive groups can be mixed and used in any ratio. In addition, a compound having a reactive double bond group and a ring-opening polymerizable compound capable of cation polymerization may be mixed and used in an arbitrary ratio.

In the photocurable composition, relative to the total amount (100% by mass) of (a) the photocurable monomer or the photocurable monomer and the binder resin, and (b) the additive having a photoreactive functional group The content of the photoreactive functional group additive is preferably 0.001% by mass to 10% by mass, more preferably 0.005% by mass to 8% by mass, and still more preferably 0.01% by mass to 5% by mass. By adjusting the amount to this range, for example, the additive can be efficiently distributed on the film surface. Furthermore, it is easy to adjust the surface free energy described later to an appropriate range. Furthermore, in the production of the uneven structure, the adhesion of the resin is suppressed in the peeling step to improve the peelability. In addition, the defects of the copy mold can be suppressed and the reusability can be improved.

As an example of the additive having a photoreactive functional group, a siloxane compound having a photoreactive functional group can be cited. More specifically, the siloxane compound of the following general formula (1) can be cited.

[化3]

In the general formula (1), R _{1 is the} same or different and represents selected from a hydrogen atom, a fluorine atom, a halogen atom, a hydrocarbon group having 1 to 20 carbons, an aryl group having 6 to 20 carbons, and an alkane having 6 to 20 carbons. Group, any atom or group in the group consisting of a polyether group with 1 to 20 carbons and a fluorocarbon group with 1 to 20 carbons _{, at least one of L 1} contains an epoxy group, a hydroxyl group, and an amino group , Vinyl ether group, lactone group, propenyl ether group, alkene group, oxetanyl group, vinyl group, acrylate group, methanol group and carboxyl group consisting of photoreactive functional group, in L ₁ is not the case where the photoreactive functional group, selected from the same or different in R ₁ represent an atom or group, n and 1-n represents the ratio of the units, typically, it represents a range of 0 to n-1.

As the siloxane compound having a photoreactive functional group, a commercially available product can be used. For example, a polysiloxane having a photoreactive functional group at the main chain end/side chain, a compound corresponding to the general formula (1), etc. can be selected from commercially available reactive group-containing silicone compounds and the like, and used. Commercial products of epoxy-containing silicone compounds include, for example, X-22-343 (manufactured by Shin-Etsu Silicone Co., Ltd.), KF-101 (manufactured by Shin-Etsu Silicone Co., Ltd.), and KF -1001 (manufactured by Shin-Etsu silicone company), X-22-2000 (manufactured by Shin-Etsu silicone company), X-22-2046 (manufactured by Shin-Etsu silicone company), KF-102 (manufactured by Shin-Etsu Silicone (manufactured by silicone company), X-22-4741 (manufactured by Shin-Etsu silicone company), KF-1002 (manufactured by Shin-Etsu silicone company), X-22-3000T (manufactured by Shin-Etsu silicone ) Company manufacture), X-22-163 (manufactured by Shin-Etsu Silicone Company), KF-105 (manufactured by Shin-Etsu Silicone Company), X-22-163A (manufactured by Shin-Etsu Silicone Company) , X-22-163B (manufactured by Shin-Etsu Silicone Company), X-22-163C (manufactured by Shin-Etsu Silicone Company), X-22-169AS (manufactured by Shin-Etsu Silicone Company), X -22-169B (manufactured by Shin-Etsu Silicone Company), X-22-173DX (manufactured by Shin-Etsu Silicone Company), X-22-9002 (manufactured by Shin-Etsu Silicone Company), SF 8411 ( Toray-Dow Corning (Toray-Dow Corning), SF 8413 (Toray-Dow Corning), SF 8421 (Toray-Dow Corning), BY16-839 (Toray-Dow Corning), BY16-839 Toray-Dow Corning (Toray-Dow Corning), BY16-876 (Toray-Dow Corning), FZ-3736 (Toray-Dow Corning), etc.

As commercially available products of hydroxyl-containing silicone compounds, specifically, for example, YF3800 (manufactured by Momentive Performance Materials Japan Co., Ltd.), XF3905 (made by Momentive Performance Materials Japan Co., Ltd.), XF3905 (Momentive Performance Materials Japan Materials Japan Co., Ltd.), X-21-5841 (manufactured by Shin-Etsu Silicone), KF-9701 (manufactured by Shin-Etsu Silicone), FM-0411 (manufactured by JNC) ), FM-0421 (manufactured by JNC), FM-0425 (manufactured by JNC), FM-DA11 (manufactured by JNC), FM-DA21 (manufactured by JNC) Company manufacturing), FM-DA26 (manufactured by JNC), FM-4411 (manufactured by JNC), FM-4421 (manufactured by JNC), FM-4425 (manufactured by JNC), JNC) manufactured by the company) and so on.

As commercially available products of amine group-containing silicone compounds, for example, KF-868 (manufactured by Shin-Etsu Silicone Co., Ltd.), KF-865 (manufactured by Shin-Etsu Silicone Co., Ltd.), and KF-864 ( Shin-Etsu Silicone (manufactured by Shin-Etsu Silicone), KF-859 (manufactured by Shin-Etsu Silicone), KF-393 (manufactured by Shin-Etsu Silicone), KF-860 (manufactured by Shin-Etsu Silicone) ), KF-880 (manufactured by Shin-Etsu Silicone), KF-8004 (manufactured by Shin-Etsu Silicone), KF-8002 (manufactured by Shin-Etsu Silicone), KF-8005 (manufactured by Shin-Etsu Silicone) (Made by silicone company), KF-862 (manufactured by Shin-Etsu silicone company), X-223820W (manufactured by Shin-Etsu silicone company), KF-869 (manufactured by Shin-Etsu silicone company), KF-861 (manufactured by Shin-Etsu Silicone), X-22-3939A (manufactured by Shin-Etsu Silicone), KF-877 (manufactured by Shin-Etsu Silicone), PAM-E (manufactured by Shin-Etsu Silicone) (Manufactured by silicone), KF-8010 (manufactured by Shin-Etsu Silicone), X-22-161A (manufactured by Shin-Etsu Silicone), X-22-161B (manufactured by Shin-Etsu Silicone) Manufactured by the company), KF-8012 (manufactured by Shin-Etsu silicone company), KF-8008 (manufactured by Shin-Etsu silicone company), X-22-1660B-3 (manufactured by Shin-Etsu silicone company), KF-857 (manufactured by Shin-Etsu Silicone), KF-8001 (manufactured by Shin-Etsu Silicone), KF-862 (manufactured by Shin-Etsu Silicone), X-22-9192 (manufactured by Shin-Etsu Silicone) (Made by silicone company), KF-868 (made by Shin-Etsu silicone company), etc.

As commercial products of the methanol group-containing silicone compound, for example, X-22-4039 (manufactured by Shin-Etsu Silicone Co., Ltd.), X-22-4015 (manufactured by Shin-Etsu Silicone Co., Ltd.), X-22-160AS (manufactured by Shin-Etsu Silicone), KF-6001 (manufactured by Shin-Etsu Silicone), KF-6002 (manufactured by Shin-Etsu Silicone), KF-6003 (manufactured by Shin-Etsu Silicone) (Manufactured by silicone company), X-22-170BX (manufactured by Shin-Etsu silicone company), X-22-170DX (manufactured by Shin-Etsu silicone company), etc.

Commercial products of carboxyl-containing silicone compounds include, for example, X-22-3701E (manufactured by Shin-Etsu Silicone Co., Ltd.), X-22-162C (manufactured by Shin-Etsu Silicone Co., Ltd.), or X -22-3710 (manufactured by Shin-Etsu Silicone) etc. Examples of commercially available products of acrylate group-containing silicone compounds include: X-22-164 (manufactured by Shin-Etsu Silicone Co., Ltd.) and X-22-174BX (manufactured by Shin-Etsu Silicone Co., Ltd.) , X-22-2426 (manufactured by Shin-Etsu silicone company), FM-0711 (manufactured by JNC), FM-0711 (manufactured by JNC), FM-0721 (manufactured by JNC), JNC), FM-7711 (manufactured by JNC), FM-7725 (manufactured by JNC), TM-0701T (manufactured by JNC), etc.

Among these, a silicone compound containing an epoxy group capable of cation polymerization and/or a silicone compound containing a hydroxyl group can be preferably selected. The weight average molecular weight (Mw) of the siloxane compound is preferably 200 to 50,000, more preferably 200 to 40,000, and still more preferably 200 to 30,000. By adjusting the molecular weight to this range, compatibility with other components in the photocurable composition improves. In addition, at the time of film formation, it is easy to obtain a twelfth minute surface deflection existence effect. The preferable range of n in General formula (1) is 0-1, More preferably, it is 0.1-1, More preferably, it is 0.3-1. It can be appropriately selected in consideration _{of the types of R 1} and L ₁ or the affinity with other components constituting the photocurable composition (compatibility, curability, reproducibility of the produced replica mold, etc.).

As another example of the additive having a photoreactive functional group, a fluorine-containing cyclic olefin polymer (specifically, a fluorine-containing cyclic olefin polymer having a photoreactive functional group at the side chain/terminal) can be cited. As a fluorine-containing cyclic olefin polymer, the specific fluorine-containing cyclic olefin polymer represented by general formula (2) can also be mentioned more specifically.

[化4]

In the general formula (2), L ₂ is selected from epoxy groups, amino groups, vinyl ether groups, lactone groups, propenyl ether groups, alcohol groups, alkene groups, oxetanyl groups, vinyl groups, and acrylate groups. At least one of R ₂ to R ₅ is selected from the group consisting of fluorine, fluorine-containing alkyl group having 1 to 10 carbon atoms, and fluorine-containing carbon number A fluorine-containing group in the group consisting of 1-10 alkoxy groups and fluorine-containing alkoxyalkyl groups having 2-10 carbon atoms. When R ₂ to R _{5 are} not fluorine-containing groups, R ₂ to R ₅ are organic groups selected from the group consisting of hydrogen, alkyl groups having 1 to 10 carbons, alkoxy groups having 1 to 10 carbons, and alkoxyalkyl groups having 2 to 10 carbons, R ₂ to R ₅ may be the same or different. In addition, R ₂ to R ₅ may be bonded to each other to form a ring structure. The dotted line indicates that the bond in this part may be a carbon-carbon single bond or a carbon-carbon double bond.

In the general formula (2), when R ₂ to R ₅ are fluorine-containing groups, specific examples include fluorine; fluoromethyl, difluoromethyl, trifluoromethyl, and trifluoroethyl , Pentafluoroethyl, pentafluoropropyl, hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro-2-methylisopropyl, perfluoro-2-methylisopropyl, n-perfluorobutyl , N-perfluoropentyl, perfluorocyclopentyl and other alkyl groups whose hydrogen part or all are substituted by fluorine; C1-10 alkyl groups; fluoromethoxy, difluoromethoxy, trifluoromethoxy , Trifluoroethoxy, pentafluoroethoxy, heptafluoropropoxy, hexafluoroisopropoxy, heptafluoroisopropoxy, hexafluoro-2-methylisopropoxy, perfluoro-2- Alkoxy groups with 1 to 10 carbon atoms in which part or all of the hydrogen of alkoxy groups such as methyl isopropoxy, n-perfluorobutoxy, n-perfluoropentoxy and perfluorocyclopentoxy are substituted with fluorine ; Fluoromethoxymethyl, difluoromethoxymethyl, trifluoromethoxymethyl, trifluoroethoxymethyl, pentafluoroethoxymethyl, heptafluoropropoxymethyl, hexafluoro Isopropoxymethyl, heptafluoroisopropoxymethyl, hexafluoro-2-methylisopropoxymethyl, perfluoro-2-methylisopropoxymethyl, n-perfluorobutoxy Alkoxyalkyl groups such as methyl group, n-perfluoropentyloxymethyl group, perfluorocyclopentyloxymethyl group, and the like are alkoxyalkyl groups having 2 to 10 carbon atoms in which part or all of hydrogen is substituted with fluorine.

R ₂ to R ₅ may be bonded to each other to form a ring structure. For example, it is possible to form a ring such as a perfluorocycloalkyl group and a perfluorocyclic ether interposed with oxygen.

When R ₂ to R _{5 are} not fluorine-containing groups _{, specific examples of R 2} to R ₅ include hydrogen; methyl, ethyl, propyl, isopropyl, 2-methylisopropyl Alkyl group, n-butyl, n-pentyl, cyclopentyl and other C1-C10 alkyl groups; methoxy, ethoxy, propoxy, butoxy, pentyloxy and other C1-C10 alkyl groups Oxy; methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentoxymethyl and other alkoxyalkyl groups having 2 to 10 carbon atoms.

_{R 2} to R _{5 in the} general formula (2) are preferably fluorine; fluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, pentafluoroethyl, heptafluoropropyl, hexafluoroiso Propyl, heptafluoroisopropyl, hexafluoro-2-methylisopropyl, perfluoro-2-methylisopropyl, n-perfluorobutyl, n-perfluoropentyl, perfluorocyclopentyl and other alkanes A fluoroalkyl group having 1 to 10 carbon atoms in which part or all of the hydrogen of the group is substituted with fluorine.

As the compound represented by the general formula (2), L ₂ can be further preferably selected as an epoxy group capable of cationic polymerization or a hydroxyl group-containing fluorine-containing cyclic olefin polymer.

When the additive having a photoreactive functional group is a fluorine-containing cyclic olefin polymer, the additive having a photoreactive functional group may include only one structural unit represented by the general formula (2), or may include the general formula (2) Two or more structural units different from each other in at least one _{of R 2} to R _5. In addition, it may be a polymer (copolymer) containing one or two or more of the structural units represented by the general formula (2) and a structural unit different from the structural unit represented by the general formula (2). The fluorine-containing cyclic olefin polymer can be obtained by appropriately applying known techniques. For example, it can be obtained by suitably applying a known technique related to ring-opening polymerization of cyclic olefins. Specific examples of polymerization conditions and catalysts used are described in Examples described later.

The olefin of the main chain in the fluorine-containing cyclic olefin polymer can preferably be selected from the fluorine-containing cyclic olefin polymer represented by the general formula (2) which forms a saturated aliphatic structure by hydrogenation. The hydrogenation rate of the main chain olefin is preferably 50% to 100%, more preferably 70% to 100%, and still more preferably 90% to 100%. When the hydrogenation rate of the main chain olefin is in the above-mentioned range, the light absorption due to the carbon-carbon double bond can be suppressed during photocuring, and the light can easily reach the deep part of the resin film. That is, the efficiency of photocuring is improved. The hydrogenation reaction can be carried out by a known method. It may be a method using a solid catalyst or a method using a homogeneous catalyst, and two or more of these catalysts may be mixed and used. Preferably, a method of using a solid catalyst can be appropriately selected, and the method can easily remove the catalyst by filtration in the post-treatment after the reaction.

The weight average molecular weight (Mw) of the fluorine-containing cyclic olefin polymer is preferably 500 to 50,000, more preferably 500 to 40,000, and still more preferably 500 to 30,000. By adjusting Mw to this range, compatibility with other components is improved, and it is easy to prepare a uniform solution. In addition, when forming a film, it is easy to effectively segregate on the surface.

(Light hardening initiator) The photocurable composition of this embodiment preferably contains a photocuring initiator. As the photohardening initiator, a photo-radical initiator that generates radicals by light irradiation, a photocationic initiator that generates cations by light irradiation, and the like can be cited.

Among the photohardening initiators, as photoradical initiators that generate radicals by light irradiation, for example, acetophenone, p-tert-butyl trichloroacetophenone, chloroacetophenone, and 2 ,2-diethoxyacetophenone, hydroxyacetophenone, 2,2-dimethoxy-2'-phenylacetophenone, 2-aminoacetophenone, dialkylaminoacetophenone Acetophenones; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-2- Benzoins such as methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one; benzophenone, benzoic acid, benzyl Methyl benzoate, methyl phthalate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxypropyl benzophenone, acrylic benzophenone, 4, Benzophenones such as 4'-bis(dimethylamino)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, diethylthioxanthone Thioxanthones such as ketones and dimethyl thioxanthone; perfluoro (tertiary butyl peroxide), perfluorobenzyl peroxide and other fluorine-based peroxides; α-acetoxime Base ester, benzyl-(o-ethoxycarbonyl)-α-monooxime, phosphine oxide, glyoxylate, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, tetramethylsulfide Thiuram, azobisisobutyronitrile, benzyl peroxide, dialkyl peroxide, t-butyl peroxypivalate, etc. In most cases, these functions are mainly manifested in the UV region where the wavelength of light is 200 nm to 400 nm.

As the photo-radical initiator that can be used preferably, there can be cited: Irgacure 651 (manufactured by Ciba Specialty Chemicals), Irgacure 184 (Ciba Specialty Chemicals) (Manufactured by Ciba Specialty Chemicals), Darocur 1173 (manufactured by Ciba Specialty Chemicals), benzophenone, 4-phenylbenzophenone, Irgacure 500 (manufactured by Ciba Specialty Chemicals), Irgacure 2959 (manufactured by Ciba Specialty Chemicals), Irgacure 127 (manufactured by Ciba Specialty Chemicals) Specialty Chemicals), Irgacure 907 (manufactured by Ciba Specialty Chemicals), Irgacure 369 (manufactured by Ciba Specialty Chemicals), Yan Irgacure 1300 (manufactured by Ciba Specialty Chemicals), Irgacure 819 (manufactured by Ciba Specialty Chemicals), Irgacure 1800 (manufactured by Ciba Specialty Chemicals) (Manufactured by Ciba Specialty Chemicals), Darocur TPO (manufactured by Ciba Specialty Chemicals), Darocur 4265 (Ciba Specialty Chemicals) Company), Irgacure OXE01 (manufactured by Ciba Specialty Chemicals), Irgacure OXE02 (manufactured by Ciba Specialty Chemicals), Isagu (manufactured by Ciba Specialty Chemicals), Irgacure OXE01 (manufactured by Ciba Specialty Chemicals), Irgacure OXE02 (manufactured by Ciba Specialty Chemicals), Esacure KT55 (manufactured by Lamberti), Esacure KIP150 (manufactured by Lamberti), Esacure KIP100F (manufactured by Lamberti), Esacure KT37 (manufactured by Lamberti), Esacure KTO 46 (manufactured by Lamberti), Esacure 1001M (manufactured by Lamberti), Esacure KIP/EM (manufactured by Lamberti), Esacure DP250 (manufactured by Lamberti), Esacure KB1 (manufactured by Lamberti), 2,4-diethyl thioxanthone, etc. Among these, as photo radical polymerization initiators that can be further preferably used, Irgacure 184 (manufactured by Ciba Specialty Chemicals), Darocur 1173 (Manufactured by Ciba Specialty Chemicals), Irgacure 500 (manufactured by Ciba Specialty Chemicals), Irgacure 819 (manufactured by Ciba Specialty Chemicals) Chemicals), Darocur TPO (manufactured by Ciba Specialty Chemicals), Esacure KIP100F (manufactured by Lamberti), Esacure ) KT37 (manufactured by Lamberti) and Esacure KTO46 (manufactured by Lamberti), etc.

Among the photocuring initiators, as a photocationic initiator that generates cations by light irradiation, any compound that initiates cationic polymerization of the ring-opening polymerizable compound capable of undergoing cation polymerization by light irradiation , There is no particular limitation. It is preferably an onium cation-an onium salt of its counter anion, which undergoes a photoreaction to release a Lewis acid. In most cases, these functions are mainly manifested in the UV region where the wavelength of light is 200 nm to 400 nm.

Examples of onium cations include diphenyl iodonium, 4-methoxydiphenyl iodonium, bis(4-methylphenyl) iodonium, bis(4-tertiary butylphenyl) iodonium, bis(ten Dialkylphenyl) iodonium, triphenyl sulfonium, diphenyl-4-thiophenoxy phenyl sulfide, bis[4-(diphenylsulfonyl)-phenyl]sulfide, bis[4-( Bis(4-(2-hydroxyethyl)phenyl)ethanyl)-phenyl)sulfide, η5-2,4-(cyclopentadienyl)[1,2,3,4,5,6- η-(methylethyl)benzene]-iron (1+) and so on. In addition, in addition to onium cations, perchlorate ions, trifluoromethanesulfonate ions, tosylate ions, trinitrotoluenesulfonate ions, and the like can also be cited. On the other hand, as a counter anion, for example, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, hexachloroantimonate, tetrakis(fluorophenyl)borate, tetrakis (Difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (perfluorophenyl) borate, tetrakis (Trifluoromethylphenyl)borate, tetrakis(bis(trifluoromethyl)phenyl)borate, etc.

As specific examples of photocationic initiators that can be further preferably used, for example, Irgacure 250 (manufactured by Ciba Specialty Chemicals), Irgacure 784 (vapor (Manufactured by Ciba Specialty Chemicals), Irgacure 290 (manufactured by BASF in Japan), Esacure 1064 (manufactured by Lamberti), Saralu (CYRAURE) UVI6990 (manufactured by Union Carbide Corporation), ADEKA Optoma SP-172 (manufactured by ADEKA), ADEKA Optoma SP-170 (made by Asahi Denka), ADEKA Optoma SP-152 (made by ADEKA), ADEKA Optoma SP-150 ( ADEKA (manufactured by ADEKA), CPI-400 (manufactured by San-Apro), CPI-310B (manufactured by San-Apro), CPI-210K (Sanya Pro (San-Apro) ), CPI-210S (manufactured by San-Apro), CPI-100P (manufactured by San-Apro), etc.

When the photocurable composition of the present embodiment includes a photocuring initiator, it may include only one type of photocuring initiator, or two or more types. On the basis of the entire photocurable composition (100% by mass), the content of the photocuring initiator in the photocurable composition is preferably 0.1% by mass to 20% by mass, more preferably 1.0% by mass to 15% by mass.

(Sensitizer) The photocurable composition of this embodiment may contain a sensitizer. Examples of sensitizers include anthracene, naphthalene, phenothiazene, perylene, thioxanthone, and benzophenone thioxanthone. Furthermore, as sensitizing dyes, thiopyrylium (thiopyrylium) salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, and thioxanthene can be exemplified. Dye, xanthene dye, xanthene dye, cyanine dye, rhodamine dye, pyrylium salt dye, etc. An anthracene-based or naphthalene-based sensitizer is preferred, and by using it in combination with a cationic curing initiator (a cationic polymerization initiator), the sensitivity is dramatically improved. Specific examples of anthracene-based or naphthalene-based compounds include dibutoxyanthracene, diethoxyanthracene, dipropoxyanthraquinone, bis(octyloxy)anthracene, diethoxynaphthalene, and the like. When a sensitizer is used, the amount of the sensitizer added is preferably 0.01% by mass to 20% by mass, and more preferably, based on the entire photocurable composition of this embodiment (100%) 0.01% by mass to 10% by mass, more preferably 0.01% by mass to 10% by mass, and multiple sensitizers may be used in combination.

(Other ingredients) The photocurable composition of this embodiment may contain components other than the above. For example, it may contain solvents, anti-aging agents, leveling agents, wettability modifiers, surfactants, plasticizers and other modifiers, ultraviolet absorbers, preservatives, antibacterial agents and other stabilizers, photosensitizers, Silane coupling agent, etc. For example, in addition to the above-mentioned target effect, the plasticizer sometimes also contributes to the adjustment of viscosity, so it is preferable.

(Physical properties of photocurable composition after curing by light irradiation) In the nanoimprinting process, for example, the following process is performed: the second photocurable composition used in the processing of the substrate to be processed and the copy mold containing the photocurable composition (first photocurable composition) The concave-convex surface is in contact, and UV irradiation is performed while applying pressure to harden and peel the second photocurable composition, thereby forming a concave-convex structure on the surface of the substrate to be processed. In this process, previously, especially when the replica mold is repeatedly used, the resin adheres to the surface of the replica mold or the shape of the uneven structure is damaged due to external stress, which prevents the repeated use of the replica mold. The inventors of the present invention conducted diligent studies on the relationship between these problems and the physical properties of the resin after curing. As a result, it was found that when the photocurable composition is used and the surface free energy of the resin surface after photocuring and the resin hardness are in the range described below, even if the replica mold is used repeatedly, the replica mold can easily maintain the original state. Achieve good processing of the processed substrate. Hereinafter, the surface free energy and resin hardness will be specifically described.

i) Regarding surface free energy In the case of the nanoimprint method using the replica mold, it is believed that the adhesion of the resin to the surface of the replica mold is achieved by designing the surface energy of the replica mold to be moderately low. Generally, as a method of knowing the surface state such as surface energy, the contact angle method of water droplets is usually used. Typically, the surface of the substrate treated with fluororesin repels water droplets, and the angle (contact angle) between the surface of the substrate and the water droplet exceeds 100°. On the other hand, on the surface of a substrate containing a material modified with a group that is easily compatible with water such as a hydroxyl group, the contact angle of water is as small as several degrees to several tens of degrees. However, in the method of evaluating the surface state of the substrate by the contact angle of water, even if the qualitative evaluation of the intermolecular force caused by the hydrogen bonding force can be carried out, it cannot be carried out between the two substances (the replica and the first (2) The various forces that act between the photocurable composition, specifically the evaluation of the hydrogen bonding force, the dispersion force, the alignment force, and the inductive force.

The inventors of the present invention have discovered that even when the contact angle of water is the same, the adhesion of the resin when used as a replica mold may be different. Based on this finding, further studies were carried out. As a result, the inventors believed that the contact angle of water is merely an index indicating the relationship with water, and it is generally difficult to judge whether it is a replica of an organic compound and a second photocurable composition. Affinity. Furthermore, with regard to other evaluation methods, it was found that the free energy of the resin film surface after photocuring (hereinafter also simply referred to as surface free energy) and the degree of adhesion of the resin during use of the replica mold are properly correlated. More specifically, if the surface free energy expressed in the form of the sum of the hydrogen bonding force, the dispersion force, the alignment force, and the inductive force acting on the surface of the resin film (replication mold) after photocuring is less than a specific value, then When the second photocurable composition is coated on the surface of the replica mold, photocured and peeled off, the residue of the second photocurable composition is unlikely to remain in the fine uneven structure on the surface of the replica mold. On the other hand, if the surface free energy exceeds a specific value, the residue of the second photocurable composition is likely to adhere, and the replica mold is likely to deteriorate and cannot be used repeatedly. The so-called "adhesion" here means that when it is remarkable, the deterioration of the surface of the replica mold after use can also be confirmed by visual inspection (more specifically, by using an optical microscope or a scanning electron microscope (Scanning Electron Microscope) , SEM) and other observations, the degree of adhesion of the second photocurable composition can be known).

Quantitatively, the surface free energy of the resin film after photocuring measured as in Evaluation Method 1 below is preferably 15 mJ/m ² to 40 mJ/m ² , and more preferably 15 mJ/m ² to 38 mJ/m ² , more preferably 15 mJ/m ² to 35 mJ/m ² . In the case where the surface free energy is greater than 40 mJ/m ² , as described above, the second photocurable composition cured by light irradiation adheres to the replica mold. In addition, when the surface free energy is less than 15 mJ/m ² , the affinity with the replica mold during coating is poor, and the second photocurable composition is easily repelled from the surface of the replica mold. Furthermore, if crimping, light irradiation, and peeling are performed in this state, for example, voids originating from air bubbles that have nowhere to escape may be generated.

[Evaluation Method 1] First, a photocurable composition is applied to a substrate to form a photocurable film, and ultraviolet rays are irradiated to obtain a cured cured film. Next, a contact angle meter was used to measure the contact angles of water, diiodomethane, and 1-bromonaphthalene with respect to the cured film. Then, calculate the surface free energy according to Kitazaki-Hata's theory.

Incidentally, in order to fully (substantially complete) curing the photocurable film, a sufficient amount of light, for example, ultraviolet rays with a cumulative light amount of ^{2000 mJ/cm 2 is irradiated.} Irradiation can be performed with UV light (Light Emitting Diode (LED) light source) with a wavelength of 365 nm. In addition, the thickness of the photocurable film in the evaluation method 1 is, for example, about 5 μm to 6 μm (5.5 μm±0.5 μm).

The calculation of the surface free energy based on Kitazaki-Hata's theory can be performed by software attached to a commercially available contact angle meter. Just in case, the following explains Kitazaki-Hata's theory in advance. When the surface free energy of the cured film of the measurement object is set to A, the component of the surface free energy A is set to the component attributable to the dispersive force (A _d ), the component attributable to the alignment (polar) force (A _p ), and the attribution Regarding the component (A _h ) of the hydrogen bonding force, A is expressed as formula (1) (the intermolecular force caused by the inductive force in the description is extremely small, so it is ignored in the calculation).

[Numerical formula 1] A=A _d +A _p +A _h formula (1)

In addition, when the surface free energy of the liquid 1 whose value of each component is known is set to B ₁ , the component of the surface free energy B ₁ is set to the component (B _1d ) attributed to the dispersing force, which is attributed to the alignment (polar) force In the case of the component (B _1p ) and the component (B _1h ) attributed to the hydrogen bonding force, B _{1 is} represented by formula (2).

[Numerical formula 2] B ₁ =B _1d +B _1p +B _1h formula (2)

Similarly, when the surface free energy of the liquid 2 whose value of each component is known is set to B ₂ , and the surface free energy of the liquid 3 whose value of each component is known is set to B ₃ , B ₂ and B ₃ respectively denote For formula (3) and formula (4).

[Numerical formula 3] B ₂ =B _2d +B _2p +B _2h formula (3) B ₃ =B _3d +B _3p +B _3h formula (4)

Furthermore, when the contact angle measured using the cured film of the measurement object and the liquid 1 is set to θ ₁ , the contact angle between the cured film of the measurement target and the liquid 2 is set to θ ₂ , and the contact angle between the cured film of the measurement target and the liquid 3 When the contact angle is set to θ ₃ , in the values of the contact angles and the respective components of the surface free energy of the cured film of the measuring object and Liquid 1, Liquid 2, and Liquid 3, equations (5), (6), and (7) ) Relationship is established.

式（5）

式（6）

式（7）[Equation 4]

Formula (5)

Formula (6)

Formula (7)

With solutions containing the formula (5), ternary simultaneous equations of formula (6) and (7) respectively calculates A _d, A _p and A _h. Then, the surface free energy A of the cured film is calculated according to equation (1).

ii) About resin hardness As a failure mode when the replica mold is repeatedly used, in addition to the resin adhesion, collapse of the uneven structure on the surface of the replica mold generated in a pressure bonding process or the like can also be cited. For example, in the case of a line and space shape, it means a line break or a gap at the edge of the line. In addition, in the case of a column shape, it indicates defects such as column breakage. Generally, the resin hardness is represented by the degree of damage by a scratch test or the pencil hardness, and the pencil hardness is represented by the hardness of a pencil when scratched with a designated pencil. However, even if these methods can be adapted to, for example, bulk evaluation of a flat surface, they cannot be adapted to the evaluation of determining the shape retention of the fine concavo-convex structure.

The inventors of the present invention found that the use of a very fine needle-like indenter to directly press into the surface of the film, and the rebound force at this time to define the hardness of the resin, the hardness obtained by the nanoimprint method becomes a suitable representation for replication. An index of the relationship between mold shape retention and resin hardness.

Specifically, the hardness of the photocurable composition after photocuring, measured as in the following evaluation method 2, is preferably 0.05 GPa to 0.5 GPa, more preferably 0.1 GPa to 0.5 GPa, and still more preferably 0.15 GPa ~0.5 GPa. When the upper limit is exceeded, the resin surface becomes hard and brittle. Even with a slight external stress, the uneven shape cannot maintain the notched shape, and cannot withstand the curvature of the roll used in the roll-to-roll process, resulting in uneven shape. crack. Furthermore, when the value is less than the lower limit, the resin is deformed due to the stress when the resin is soft and the second photocurable composition is in contact with the liquid and pressure-bonded, for example, the shape of the T-top may change. Anchoring effect and cannot be peeled off.

[Evaluation Method 2] First, the cured film was obtained by the same method as the above-mentioned evaluation method 1. Next, a nanoindenter is used to press a Bosch indenter against the cured film, and the hardness is calculated based on the value of the detected stress.

＜Concave-convex structure and its manufacturing method＞ The photocurable composition of this embodiment can be used to produce an uneven structure (for example, a replica mold) including a substrate and a resin layer on which the resin layer is provided with fine unevenness formed on the surface. Hereinafter, the specific aspect or production method of the substrate will be described in detail.

·About the substrate The raw material of the substrate is not particularly limited. The substrate contains, for example, an organic material or an inorganic material. In addition, regarding the shape of the substrate, for example, a sheet-like, film-like, plate-like, or porous-like substrate can be used.

More specifically, when the substrate contains an organic material, for example, polyacetal, polyamide, polycarbonate, polyphenylene ether, polybutylene terephthalate, polyethylene terephthalate , Polyesters such as polyethylene naphthalate; Polyolefins such as polyethylene and polypropylene; Poly(meth)acrylate, polyether, polyether sulfide, polyphenylene sulfide, polyether ether ketone, polyimide , Polyether imide, polyacetate cellulose, polyvinyl alcohol, polyurethane, polyvinylidene fluoride, polytetrafluoroethylene, hexafluoropropylene-tetrafluoroethylene copolymer, perfluoropropyl ethylene One or two or more of various resins such as fluororesin, such as base ether-tetrafluoroethylene copolymer, are used as raw materials. Moreover, the substrate can be made by processing raw materials by methods such as injection molding, extrusion molding, hollow molding, thermoforming, and compression molding. In addition, as a porous substrate, for example, a substrate hardened in a state of being porous by a foaming agent, a substrate made porous by stretching a non-porous base material, and A substrate made by laser processing to be porous, a non-woven fabric with a porous structure between fibers, etc.

In addition, as another aspect, the substrate may be cured by light irradiation in the presence of a polymerization initiator to cure a photocurable monomer such as (meth)acrylate, styrene, epoxy, and oxetane. Single-layer substrates, or substrates formed by coating such photocurable monomers on organic or inorganic materials.

When the substrate contains an inorganic material, as its constituent material, for example, copper, gold, platinum, nickel, aluminum, silicon, stainless steel, quartz, soda glass, sapphire, carbon fiber, etc. can be cited.

Regardless of whether the constituent material of the substrate is an organic material or an inorganic material, in order to improve the adhesion with the photocurable composition and its cured product, some treatment may be performed on the surface of the substrate. Examples of such treatment include corona treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, and adhesion treatment such as easy adhesion coating treatment. In addition, regardless of whether the constituent material of the substrate is an organic material or an inorganic material, the substrate may be a single layer, or may have a structure of two or more layers.

The substrate is preferably a resin film. The substrate is preferably, for example, a resin film containing any of the above-mentioned resins. Since the substrate is a resin film instead of an inorganic material, the user can easily cut it into a desired shape or size for use. In addition, there is an advantage that the layered body can be rolled up when storing the layered body, that is, it is space-saving.

As another viewpoint, the light transmittance of the substrate is preferably high. Thereby, the following advantages can be obtained: (i) when manufacturing a concave-convex structure, the hardening reaction can be promoted by exposure to light from the side of the substrate; or (ii) various types can be easily confirmed by visual inspection. Step; or (iii) It is easy to freely design the direction of light irradiation and increase the freedom of device design. From the viewpoint of (i), it is sometimes preferable that the substrate has a high transmittance in the wavelength region of light with which the photohardening initiator reacts. More preferably, the transmittance of light in the ultraviolet region is high. For example, the transmittance of light with a wavelength of 200 nm to 400 nm is preferably 50% to 100%, more preferably 70% to 100%, and still more preferably 80% to 100%. From the viewpoint of (ii), it is preferable that the transmittance of light in the visible region of the substrate is high. For example, the transmittance of light with a wavelength of 500 nm to 1000 nm is preferably 50% to 100%, more preferably 70% to 100%, and still more preferably 80% to 100%. By the way, most resin films have high transparency, so in terms of light transmittance, it can also be said that a resin film is preferable as a substrate.

The thickness of the substrate is not particularly limited. It can be appropriately adjusted according to various purposes, for example, the degree of operability of the laminate, the dimensional accuracy of the concavo-convex structure to be obtained, and the like. The thickness of the substrate is, for example, 1 μm to 10000 μm, specifically 5 μm to 5000 μm, and more specifically 10 μm to 1000 μm. The shape of the entire substrate is not particularly limited. For example, it may be plate-shaped, disk-shaped, roll-shaped, or the like.

·About coating steps The specific procedure of the manufacturing method of the concavo-convex structure of this embodiment is not particularly limited. For example, it can manufacture by the process including the process (photocurable layer formation process) of forming a photocurable composition layer on the surface of a board|substrate using the photocurable composition of this embodiment. The specific method of the step of forming the photocurable composition layer is not particularly limited. Typically, first, the photocurable composition is coated on the substrate by the following coating method to form the photocurable layer.

Regarding the coating method, a known method can be applied. Examples include: table coating method, spin coating method, dip coating method, die coating method, spray coating method, bar coating method, roll coating method, curtain flow coating method, slit coating method, knife coating Cloth method, inkjet coating method, dispense method, etc. These coating methods can be appropriately selected in consideration of the shape or size of the fine concavities and convexities, the size of the replica mold, productivity, and the like.

In addition, when the photocurable composition contains a solvent, for the purpose of removing the solvent, a baking (heating) step may be provided after coating as necessary. Regarding the various conditions such as the baking temperature and time, it may be appropriately set in consideration of the coating thickness, process style, and productivity. It is selected within a temperature range of preferably 20°C to 200°C, more preferably 20°C to 180°C, and within a time period of 0.5 minutes to 30 minutes, more preferably 0.5 minutes to 20 minutes. The baking method can be any of the following methods: direct heating by a hot plate or the like; passing in a hot air stove; using an infrared heater or the like.

The thickness of the photocurable layer provided on the substrate is preferably in the range of 0.05 μm to 100 μm, more preferably in the range of 0.10 μm to 80 μm, and still more preferably in the range of 0.20 μm to 50 μm. By setting the thickness of the photocurable layer within the above-mentioned range, the photocuring of the photocurable composition at the time of making the replica mold can be effectively performed. In addition, for example, considering the roll-to-roll process, even if a bending stress corresponding to the bending rate of the roll that is wound around the replica mold is applied, it can be used in a good state without the occurrence of cracks.

·About crimping steps The uneven surface of the mold having the uneven structure on the surface is press-bonded to the photocurable layer formed on the substrate by the above method. Thereby, the uneven pattern corresponding to the uneven surface of the mold is transferred to the photocurable layer. By the way, the mold here is a mold designed based on the uneven processing of the substrate to be processed, specifically a master mold.

The shape of the mold (master mold) is not particularly limited. Regarding the shape of the convex and concave portions of the mold, a dome shape, a quadrangular prism shape, a cylindrical shape, a prism shape, a quadrangular pyramid shape, a triangular pyramid shape, a polyhedron shape, a hemispherical shape, and the like can be mentioned. Regarding the cross-sectional shape of the convex portion and the concave portion of the mold, a quadrangular cross-section, a triangular cross-section, a semicircular cross-section, and the like can be cited. The width of the convex portion and/or concave portion of the mold (master mold) is not particularly limited, and is, for example, 10 nm to 100 μm, preferably 20 nm to 70 μm. In addition, the depth of the concave portion and/or the height of the convex portion is not particularly limited, and is, for example, 10 nm to 100 μm, preferably 20 nm to 70 μm. Furthermore, the ratio of the width of the convex portion to the height of the convex portion, that is, the aspect ratio, is preferably 0.1 to 500, and more preferably 0.5 to 20.

As the material of the mold (master mold), for example, metal materials such as nickel, iron, stainless steel, germanium, titanium, and silicon; inorganic materials such as glass, quartz, and alumina; polyimide, polyamide, polyester, etc. Polycarbonate, polyphenylene ether, polyphenylene sulfide, polyacrylate, polymethacrylate, polyarylate, epoxy resin, silicone resin and other resin materials; carbon materials such as diamond and graphite.

Regarding the method of crimping, a known method can be used. For example, a method of pressing with an appropriate pressure in a state where the photocurable composition layer is in contact with the uneven pattern of the mold is exemplified. The upper limit of the pressure is not particularly limited. The upper limit of the pressure is, for example, preferably 10 MPa or less, more preferably 5 MPa or less, and particularly preferably 1 MPa or less. The pressure can be appropriately selected according to the pattern shape, aspect ratio, material, etc. of the mold. The lower limit of pressure does not particularly exist. It is sufficient that the photocurable composition layer is filled in each corner corresponding to the concave-convex pattern of the mold. The upper limit of the pressure is, for example, 0.1 MPa or more.

The crimping step can be performed under the atmosphere, or under vacuum, inert gas such as nitrogen, and fluorine gas environment. It can be selected in a timely manner according to the curability of the photocurable composition, degassing such as exhaust, and improvement of the filling speed of the photocurable composition.

·Light irradiation steps In the light irradiation step, light is irradiated to the photocurable layer. More specifically, the photocurable layer is irradiated with light in a state where pressure is applied in the pressure bonding step (in the state of the pressure bonding mold). Then, the photocurable layer is cured.

The light to be irradiated is not particularly limited as long as it can harden the photocurable composition layer. Specifically, ultraviolet rays, visible rays, infrared rays, and the like can be cited. Among these, it is preferable to cause the light to generate radicals or ions from the photohardening initiator. As the light source, specifically, a light source that generates light with a wavelength of 400 nm or less can be used. For example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, and a black light lamp can be used. , Microwave excited mercury lamp, metal halide lamp, i-ray, g-ray, KrF excimer laser light, ArF excimer laser light, etc. The cumulative light amount of light irradiation can be set to 3 mJ/cm ² to 10000 mJ/cm ^{2, for example} .

The light irradiation can be performed in either direction from the back surface of the substrate on which the photocurable composition layer is formed or the surface of the mold (master mold) opposite to the surface on which the concavo-convex structure is formed. In particular, it is only necessary to consider the material (transmittance of light, etc.) of the substrate or the mold and select it at the appropriate time.

For the purpose of accelerating the curing of the photocurable composition layer, light irradiation and heating may be used in combination. And/or the heating step may be performed after the light irradiation step. The heating temperature is preferably room temperature (usually 25°C) or higher and 200°C or lower, and more preferably room temperature or higher and 150°C or lower. Regarding the heating temperature, it may be appropriately selected in consideration of the heat resistance of the substrate, the photocurable composition layer, and the mold, or the increase in productivity due to hardening acceleration, and the like.

·About the peeling step The manufacturing method of the concavo-convex structure of this embodiment preferably includes a mold peeling step. Specifically, the photocurable layer hardened by the light irradiation step is separated from the mold to obtain a concavo-convex structure in which a concavo-convex pattern is formed on the substrate. Regarding the method of mold peeling, a known method can be applied. For example, the end of the substrate can be used as a starting point to peel the resin delamination formed on the substrate from the mold. In addition, an adhesive tape may be attached to the substrate, and the resin layer formed on the substrate may be separated from the mold using the tape as a starting point. Furthermore, when it is implemented by a continuous method such as a roll-to-roll method, it may also be a method in which the roll is rotated at a speed corresponding to the circumferential speed of the step, and the resin delamination and unevenness formed on the substrate The patterned concavo-convex structure is peeled while being rolled up. Through the above steps, a concave-convex structure in which the concave-convex structure of the mold (mother mold) is reversed can be manufactured.

(How to use copy mode) The method of using the copy mold is not particularly limited. For example, it can be used in the same way as the method of making the replica mold. In this case, the mold called the master mold is replaced with a mold (replica mold) that hardens the photocurable composition (first photocurable composition) of the present embodiment and has a concave-convex structure on the surface. . In addition, as a photocurable composition (second photocurable composition), it can be selected to have characteristics corresponding to the processing method of the substrate to be processed or various applications (for example, etching resistance, transparency, hardness, gas permeability, etc.) s material. Furthermore, the replica mold containing the photocurable composition of the present invention may be used repeatedly in the same material (first photocurable composition). For example, the first photocurable composition is used to create 50 replica molds from the replica mold, and 100 substrates are processed using each replica mold and the second photocurable composition. As a result, 5,000 (50×100) substrates can be processed, the deterioration of the copy mold can be prevented, and the product can be manufactured efficiently.

Regarding the processing of the substrate to be processed, for example, the circuit formation will be described as an example, and a method of forming a copper-embedded trench on the surface of a silicon wafer can be exemplified. Specifically, it is as follows. First, a photocurable composition having etching resistance is coated on a silicon wafer by spin coating or the like, and the replica mold of the present invention is crimped, and the photocurable composition is cured by light irradiation and peeled off. Secondly, with the uneven structure formed on the silicon wafer as a mask, the surface of the silicon wafer is processed by a dry etching method to form the uneven structure. Then, copper is buried to complete the circuit.

In such a process, if the copy mold can be used repeatedly, the number or area of the processed substrate that can be processed from a copy mold can be increased, and the productivity can be improved. In short, a substrate including a resin layer with fine concavities and convexities formed on the surface of the photocurable composition of the present embodiment is repeatedly used as a replica mold to form fine concavo-convex patterns, thereby improving the productivity of nanoimprinting. . That is, by using the photocurable composition of this embodiment, a UV-type nanoimprint process with high industrial productivity can be realized.

In addition, regarding the findings of the present inventors, the photocurable composition of the present embodiment has the following characteristics: the adaptable width of the pattern shape is from nanometer to micrometer size. Thereby, in addition to the use of the replica mold, the photocurable composition of the present embodiment can also be preferably used for applications other than the replica mold (a photocurable composition can be used to form various fine concavo-convex patterns well).

The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than those described above can be adopted. In addition, the present invention is not limited to the above-mentioned embodiments, and modifications, improvements, etc. within the scope of achieving the object of the present invention are included in the present invention. [Example]

The implementation aspects of the present invention will be described based on examples. In addition, the present invention is not limited to the examples.

First, the following will be explained. ·Analysis method of commercially available products and synthesized light-curing additives or binder resins ·Surface free energy measurement method (evaluation method 1), hardness measurement method (evaluation method 2) ·In the nanoimprinting process, the molds, devices, evaluation/analysis methods, etc. used

[Weight average z (Mw) and molecular weight distribution (Mw/Mn)] The molecular weights of the additives shown in the below-mentioned commercially available products and synthesis examples were measured by gel permeation chromatography (GPC). Specifically, under the following conditions, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer dissolved in tetrahydrofuran (Tetrahydrofuran, THF) are corrected by polystyrene standards and measured . ·Detector: RI-2031 and 875-UV manufactured by JASCO Corporation ·Tandem connection string: Shodex K-806M, 804, 803, 802.5 ·Column temperature: 40℃ ·Flow rate: 1.0 ml/min ·Sample concentration: 3.0 mg/mL～9.0 mg/mL

[Hydrogenation rate of fluorine-containing cyclic olefin polymer] The powder of the additive subjected to the hydrogenation reaction was dissolved in deuterated tetrahydrofuran. For the obtained, the integral of the signal of hydrogen bonded to the double-bonded carbon of the main chain with δ=4.5 ppm～7.0 ppm was obtained by 270 MHz- ^{1 H-nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) measurement} Value, and calculate the hydrogenation rate based on the integral value. In the case where a signal of hydrogen originating from a double bond of the main chain is not observed in the region of δ=4.5 ppm to 7.0 ppm, the hydrogenation rate is set to 100%.

[Evaluation method 1: Surface free energy measurement method] Used on a polyethylene terephthalate (PET) film substrate (Lumirror U34, thickness 188 μm, manufactured by Toray) The bar coater forms a film of the photocurable composition. When the photocurable composition contains a solvent, it is then dried on a hot plate at 100°C for 1 minute. Thereby, a photocurable film is formed. Next, UV light (LED light source) with a wavelength of 365 nm was irradiated with a cumulative light amount of 2000 mJ/cm ² to harden the photocurable film to produce a sample for measuring surface free energy with a uniform surface with a thickness of 5 μm to 6 μm.

A contact angle meter (A-XE type) manufactured by Kyowa Interface Chemical Co., Ltd., and water, diiodomethane, and 1-bromonaphthalene as standard test solutions were used to measure the contact angle of the sample surface. In order to calculate the surface free energy, the calculation method based on the Kitazaki-Hata theory is used, and the known surface free energy of the standard test liquid and the measured value of the contact angle of the standard test liquid on the object are used for calculation. Specifically, FAMAS (manufactured by Kyowa Interface Chemical Co., Ltd.), which is an application software attached to the contact angle meter, is used in the calculation. The numerical values described in the examples are the average values of the results obtained by performing the same test five times on one sample.

[Evaluation method 2: Hardness measurement method] First, formation of a photocurable film and light irradiation were performed by the same method as the evaluation method 1, and a cured film of the photocurable composition was obtained. Secondly, using a nano indenter (TI-950 Tribo Indenter, manufactured by Hysitron Inc.), based on the standard of the nano indentation method, that is, ISO14577 Indentation test to determine resin hardness. For the cured film, press the Bosnian indenter to a depth of 200 nm, and calculate the hardness (GPa) at room temperature from 23°C to 25°C based on the detected stress value. The numerical values described in the examples are the average values of the results obtained by performing the same test five times on one sample.

[The mold used (equivalent to the master mold)] Use a quartz mold with a pattern of linear lines (convex parts) and spaces (concave parts). Specifically, when the width of the convex portion is L1, the width of the concave portion is L2, and the height of the convex portion is L3, the following mold A and mold B are used. ·Mold A: L1=450 nm, L2=450 nm, L3=450 nm ·Mold B: L1=75 nm, L2=75 nm, L3=150 nm

[Apparatus used in the production of concavo-convex structure] The light-curable composition (photocurable film) and the mold are crimped and the subsequent UV irradiation uses the UV-type nanoimprinting device X-100U (manufactured by Scivax). The UV light source is a UV-LED light source with a wavelength of 365 nm.

[Measurement of the size of the convex part] A scanning electron microscope JSM-6701F (manufactured by JASCO Corporation, hereinafter referred to as SEM) was used for the size measurement of the uneven structure. Regarding the measurement of the convex portion width, the line width of any five locations on the pattern surface is measured, and the average value of the obtained five values is used as the convex portion width.

[Evaluation of the size of the convex part when used repeatedly as a copy mold] In order to evaluate the deterioration of the mold accompanying repeated use, the width of the convex portion of the replica mold after use was measured by SEM at the time of mold production, when it was used once, and every 10 times. In Table 2 described later, unless otherwise specified, the measured value of the width of the convex portion after 50 uses is described.

Hereinafter, the synthesis method of the additive and the binder resin having the photoreactive functional group, the preparation method of the photocurable composition, and the evaluation result will be described.

[Synthesis Example 1] Synthesis of Additive (C-1) First, prepare 5,5,6-trifluoro-6-(trifluoromethyl)bicyclo[2.2.1]heptane as a fluorine-containing cyclic olefin monomer -2-ene (100 g) and 1,2-epoxy-5-hexene (5.675 g) in tetrahydrofuran. A tetrahydrofuran solution of Mo(N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHCMe ₂ Ph)(OBut) ₂ (85 mg) was added to this solution, and the ring-opening metathesis polymerization was carried out at 70°C. Next, using palladium alumina (5 g) as a solid catalyst, the olefin part of the obtained polymer was subjected to a hydrogenation reaction at 160° C. for 24 hours to hydrogenate the olefin in the main chain. The palladium alumina was removed by pressure filtration of the obtained solution with a filter with a pore diameter of 0.5 μm, and the obtained solution was discharged into a methanol/hexane (50% by mass/50% by mass) mixed solution. The white polymer is separated by filtration and dried. As described above, 95 g of a white powdery polymer (additive (C-1)) was obtained.

According to ¹ H-NMR, the hydrogenation rate of the additive (C-1) is 100%. In the structure represented by the general formula (2), L ₂ contains a hydroxyl group-containing aliphatic structure in which an epoxy group is reduced by hydrogen. The weight average molecular weight (Mw) is 6050, and the molecular weight distribution (Mw/Mn) is 1.49.

[Synthesis Example 2] Synthesis of Additive (C-2) First, the type of monomer was changed to 5,6-difluoro-5-trifluoromethyl-6-perfluoroethylbicyclo[2.2.1]hept- Except for this, the same method as in Synthesis Example 1 was used to carry out ring-opening metathesis polymerization. Next, using (Ph ₃ P) ₃ CORuHCl as a homogeneous catalyst, the olefin portion of the obtained polymer was subjected to a hydrogenation reaction at 125° C. for 24 hours to hydrogenate the olefin in the main chain. Then, the obtained solution was discharged into methanol, and the white polymer was separated by filtration and dried to obtain 98 g of a white powdery polymer (additive (C-2)). According to ¹ H-NMR, the hydrogenation rate of the additive (C-2) is 100%, and in the structure represented by the general formula (2), L ₂ contains an epoxy group-containing aliphatic structure. The weight average molecular weight (Mw) is 6200, and the molecular weight distribution (Mw/Mn) is 1.51.

[Synthesis example 3] Synthesis of binder resin (B-1) First, prepare 5,5,6-trifluoro-6-(trifluoromethyl)bicyclo[2.2.1]hept-2-ene (100 g) With 1-hexene (0.298 mg) in tetrahydrofuran. A tetrahydrofuran solution of Mo(N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHCMe ₂ Ph)(OBut) ₂ (50 mg) was added to this solution, and ring-opening metathesis polymerization was carried out at 70°C. Then, using palladium alumina (5 g), the olefin part of the obtained polymer was hydrogenated at 160°C to obtain poly(1,1,2-trifluoro-2-trifluoromethyl-3,5). -Cyclopentylethylene) in tetrahydrofuran. The palladium alumina was removed by pressure filtration of the obtained solution with a filter with a pore diameter of 5 μm. Then, the obtained solution was added to methanol, and the white polymer was separated by filtration and dried. Thereby, 99 g of a binder resin (B-1) of a fluorine-containing cyclic olefin polymer which is a non-reactive functional group was obtained. The hydrogenation rate of the binder resin (B-1) was 100%, the weight average molecular weight (Mw) was 70,000, and the molecular weight distribution (Mw/Mn) was 1.71.

[Example 1] Preparation of photocurable composition (1), production of replica mold, etc. First, the following solution was prepared: bis(3-ethyl-3-oxetanylmethyl) as a photocurable monomer 10 g of a mixture of ether and 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate in a mass ratio of 7/3, add X-22-2000 as an additive (Manufactured by Shin-Etsu Silicone) 0.05 g and 1 g of CPI-310B (manufactured by San-Apro) as a light hardening initiator. (X-22-2000 is represented in the general formula (1) where R ₁ = methyl, L ₁ = epoxy, methyl and phenyl, molecular weight (Mw) is 7300) Then, use a filter with a pore size of 1 μm to This solution was pressure-filtered, and then filtered with a filter with a pore size of 0.1 μm. The photocurable composition (1) was prepared as described above.

Using the obtained photocurable composition (1), according to Evaluation Method 1 and Evaluation Method 2, a resin film cured with an LED light source was produced and evaluated. The surface free energy is 26.2 mJ/m ² , and the surface hardness is 0.28 GPa.

After forming a film on the PET substrate with the photocurable composition (1) by the same method as the evaluation method 1, using the nanoimprinting device, the atmospheric surface was press-bonded to the mold A or the mold at a pressure of 0.2 MPa gauge pressure. Mold B. While maintaining the pressure applied, light was irradiated with a cumulative light quantity of ^{2000 mJ/cm 2} from the back side of the PET film substrate to cure the photocurable composition (1). The cured film formed on the PET film substrate was peeled from the mold to obtain a replica A-1 (made from the quartz mold A) or a replica B-1 (made from the quartz mold B) with a line and space structure on the surface. SEM was used to measure the width of the convex part of the produced replica mold. The replica mode A-1 is 449 nm, and the replica mode B-1 is 74 nm. Furthermore, the cross section of the replica B-1 was cut out, and the state of the element ions in the cross section was mapped by TOF-SIMS. As a result, the cross-sectional state of the two layers was observed, and the negative ions of the X-22-2000 silicon-containing fragments belonging to the additive were detected on the atmospheric surface side of the two layers (shown in Fig. 1).

[Example 2] Preparation of photocurable composition (2), preparation of replica mold, etc. Prepare the following solution: bis(3-ethyl-3-oxetanylmethyl) ether as a photocurable monomer and 3,4-epoxycyclohexylmethyl-3',4'-epoxy To 9.5 g of a mixture of cyclohexane carboxylate with a mass ratio of 7/3, 0.5 g of the additive (C-1) synthesized in Synthesis Example 1 as an additive and CPI-310B (Sanya) as a light hardening initiator were added Pro (manufactured by San-Apro) 0.95 g solution. Then, it prepared in the same manner as in Example 1 to prepare a photocurable composition (2).

Using the obtained photocurable composition (2), according to Evaluation Method 1 and Evaluation Method 2, a resin film cured with an LED light source was produced and evaluated. The surface free energy is 32.0 mJ/m ² , and the surface hardness is 0.22 GPa. In addition, the width of the convex portion of the replica A-2 produced by the same method as in Example 1 was 449 nm, and the width of the convex portion of the replica B-2 was 73 nm.

[Example 3] Preparation of photocurable composition (3), preparation of replica mold, etc. A photocurable composition (3) was prepared in the same manner as in Example 1, except that 0.1 g of X-22-2000 (manufactured by Shin-Etsu Silicone Co., Ltd.) and 0.05 g of the additive (C-1) were used as additives .

Using the obtained photocurable composition (3), according to Evaluation Method 1 and Evaluation Method 2, a resin film cured with an LED light source was produced and evaluated. The surface free energy is 36.8 mJ/m ² and the hardness is 0.25 GPa. In addition, the width of the convex portion of the replica A-3 produced by the same method as in Example 1 was 450 nm, and the width of the convex portion of the replica B-2 was 75 nm.

[Example 4] Preparation of photocurable composition (4), production of replica molds, etc. The following solutions were prepared: 10 g of limonene dioxide as a photocurable monomer was added as an additive BY16-876 (East Toray-Dow Corning (manufactured by Toray-Dow Corning) 0.1 g and additive (C-1) 0.05 g, CPI-310B (manufactured by San-Apro) as a light hardening initiator 0.5 g, and sensitization (Anthracure UVS-1331, manufactured by Kawasaki Chemical Industry Co., Ltd.) 0.1 g. (BY16-876 is represented in the general formula (1) where R ₁ = methyl, L ₁ = epoxy, methyl, and polyether group, and the molecular weight (Mw) is 25000) Then, it was prepared in the same manner as in Example 1 to obtain Light-curable composition (4).

Using the obtained photocurable composition (4), according to Evaluation Method 1 and Evaluation Method 2, a resin film cured with an LED light source was produced and evaluated. The surface free energy is 33.2 mJ/m ² and the hardness is 0.24 GPa. In addition, the width of the convex portion of the replica A-4 produced by the same method as in Example 1 was 448 nm, and the width of the convex portion of the replica B-4 was 74 nm.

[Example 5] Preparation of photocurable composition (5), preparation of replica mold, etc. Prepare the following solution: bis(3-ethyl-3-oxetanylmethyl) ether as a photocurable monomer and 3,4-epoxycyclohexylmethyl-3',4'-epoxy To 10 g of a mixture of cyclohexane carboxylate with a mass ratio of 7/3, 2.5 g of the binder resin (B-1) synthesized in Synthesis Example 3 and X-22-2000 (Shin-Etsu Silicone (Shin-Etsu Silicone ( Silicone) 0.05 g and 1 g of CPI-310B (manufactured by San-Apro) as a photohardening initiator. Then, it adjusted similarly to Example 1, and obtained the photocurable composition (5).

Using the obtained photocurable composition (5), according to Evaluation Method 1 and Evaluation Method 2, a resin film cured with an LED light source was produced and evaluated. The surface free energy is 34.2 mJ/m ² and the hardness is 0.23 GPa. In addition, the width of the convex portion of the replica A-5 produced by the same method as in Example 1 was 450 nm, and the width of the convex portion of the replica B-5 was 74 nm.

[Example 6] Preparation of photocurable composition (6), preparation of replica mold, etc. A photocurable composition (6) was obtained in the same manner as in Example 2 except that the additive (C-2) synthesized in Synthesis Example 2 was used as an additive.

Using the obtained photocurable composition (6), according to Evaluation Method 1 and Evaluation Method 2, a resin film cured with an LED light source was produced and evaluated. The surface free energy is 28.5 mJ/m ² and the hardness is 0.25 GPa. In addition, the width of the convex portion of the replica A-6 produced by the same method as in Example 1 was 448 nm, and the width of the convex portion of the replica B-6 was 74 nm.

[Example 7] Preparation of the photocurable composition (7), production of replica molds, etc. X-22-2000 (Shin-Etsu silicone) was used as an additive of the photocurable composition (3) of Example 3 Except that it was changed to FM-DA11 (manufactured by JNC), the photocurable composition (7) was obtained by the same method as in Example 3. Using the obtained photocurable composition (7), according to Evaluation Method 1 and Evaluation Method 2, a resin film cured with an LED light source was produced and evaluated. The surface free energy is 25.7 mJ/m ² and the hardness is 0.27 GPa. In addition, the width of the convex portion of the replica A-7 produced by the same method as in Example 1 was 448 nm, and the width of the convex portion of the replica B-7 was 74 nm.

[Evaluation of repeated usability as a copy model in different materials] · Example of repeated use evaluation using the replica model A-1 and the replica models (A-2 to A-7) produced in Example 2 to Example 7: First, a hydrophilized alkali-free glass substrate is prepared: a hydrophilized alkali-free glass substrate is hydrophilized by a nitrogen atmosphere piezoelectric slurry treatment to hydrophilize the alkali-free glass substrate so that the water contact angle becomes 4° or less. Next, on the substrate, a commercially available nanoimprint material (PAK-01, manufactured by Toyo Gosei Co., Ltd.) was applied as the second photocurable composition by a spin coating method.

Using the nanoimprinting device, the uneven surface of the replica A-1 was crimped to the obtained coating film surface under a gauge pressure of 0.2 MPa. While maintaining the pressure, the back side of the replica mold was irradiated with light with an accumulated light amount of ^{6000 mJ/cm 2 to harden the coating film.} Then, the copy mold A-1 was peeled off to obtain a transfer body A-1 (made from the copy mold A-1) containing the second photocurable composition with the uneven structure formed on the surface.

The reusability of the replica mold A-1 was evaluated by repeating the steps of applying the second photocurable composition to the alkali-free glass substrate to peeling off the replica mold A-1. The width of the convex part of the replica A-1 after 50 times of repeated use was measured by SEM, and the result was 449 nm. That is, the width of the convex portion at the time of production (before use as a replica mold) did not change.

· Example of repeated use evaluation using the replica B-1 made in Example 1 and the replica molds (B-2 to B-7) made in Example 2 to Example 7: Except for replacing the used copy mold, each copy mold was repeatedly used 50 times by the same method as the copy mold A-1. The width of the convex portion of the replicated mold after repeated use was measured, and the width of the convex portion at the time of production did not change in any of the replicated molds.

According to the above, even if the same photocurable composition as the material used to make the replica mold is used, it can be used repeatedly. That is, the copy mold can be used repeatedly in different materials.

[Evaluation of repeated usability as a copy model in the same material] · Example of repeated use evaluation using the replica A-1 made in Example 1 and the replica molds (A-2 to A-7) made in Example 2 to Example 7: On the PET substrate, the photocurable composition (1) used in Example 1 as the second photocurable composition was coated by a spin coating method.

Using the nanoimprinting device, the uneven surface of the replica A-1 was crimped to the obtained coating film surface under a gauge pressure of 0.2 MPa. While maintaining the pressure, the back side of the replica mold was irradiated with light with an accumulated light amount of ^{6000 mJ/cm 2 to harden the coating film.} Then, the copy mold A-1 was peeled off, thereby obtaining a transfer body A-1 (according to the copy mold) containing the photocurable composition (1) as the second photocurable composition and the same material with the uneven structure formed on the surface. A-1 and produced).

The repeatability of the replica A-1 was evaluated by repeating the self-coating as the second photocurable composition of the photocurable composition (1) used in Example 1 Go to the step of peeling off the replica A-1.

The width of the convex part of the replica A-1 after 50 times of repeated use was measured by SEM, and the result was 449 nm. That is, there is no change in the width of the convex portion at the time of production (before use as a replica mold), and there is no defect in appearance. Except for replacing the used copy mold, each copy mold was repeatedly used 50 times by the same method as the copy mold A-1. The width of the convex portion of the replica mold after repeated use was measured. As a result, in any replica mold, the width of the convex portion during production did not change, and there was no defect in appearance.

· Example of repeated use evaluation using the replica B-1 made in Example 1 and the replica molds (B-2 to B-7) made in Example 2 to Example 7: Except for replacing the used copy mold, each copy mold was repeatedly used 50 times by the same method as the copy mold A-1. The width of the convex portion of the replica mold after repeated use was measured. As a result, in any replica mold, the width of the convex portion during production did not change, and there was no defect in appearance.

According to the above, even if the same photocurable composition as the material used to make the replica mold is used, it can be used repeatedly. That is, the copy mold can be used repeatedly in the same material.

[Comparative Example 1] Preparation of photocurable composition (8), etc. The following solution was prepared: a solution of 0.2 g of Irgacure 184 (manufactured by BASF) as a light hardening initiator added to 10 g of methyl methacrylate as a light hardening monomer . Then, it prepared in the same manner as in Example 1 to obtain a photocurable composition (8).

Using the obtained photocurable composition (8), according to Evaluation Method 1 and Evaluation Method 2, a resin film cured with an LED light source was produced and evaluated. The surface free energy is 42.7 mJ/m ² and the hardness is 0.35 GPa. The width of the convex portion of the replica A-8 produced by the same method as in Example 1 was 405 nm, and the width of the convex portion of the replica B-8 was 68 nm. In addition, the same method as the above-mentioned "Evaluation of Repeatability as a Copy Model in Different Materials" was used to evaluate the repeatability. After both the replica A-8 and the replica B-8 were used once, the residue of the second photocurable composition adhered to an extent that was visually apparent. In addition, the result of SEM observation was that the residue of the second photocurable composition adhered between the buried wire and the wire. Furthermore, the same method as the above-mentioned "evaluation of repeatability in the same material as a replica mold" was used to evaluate the repeatability, but the replica mold A-8 or the replica mold B-8 was compared with the photocuring properties. At the moment when the composition (8) is in contact, the hardened resin layer of the replica mold is dissolved and the next step cannot be carried out. That is, it cannot be used repeatedly in the same material.

[Comparative Example 2] Preparation of photocurable composition (9), etc. The following solution was prepared: a combination of pentaerythritol triacrylate (KAYARAD)-PET-30 (manufactured by Nippon Kayaku Co., Ltd.) as a photocurable monomer and multifunctional acrylate polymer BS371 (manufactured by Arakawa Chemical Industry Co., Ltd.) Add 0.4 g of Irgacure 184 (manufactured by BASF) as a light hardening initiator to 10 g of a mixture with a mass ratio of 4/1, and dissolve it in methyl acetate and methyl ethyl ketone (Methyl Ethyl Ketone, MEK) is a solution of 10 g of a mixture with a mass ratio of 3/2. Then, filtration was performed in the same manner as in Example 1 to prepare a photocurable composition (9).

Using the obtained photocurable composition (9), according to Evaluation Method 1 and Evaluation Method 2, a resin film cured with an LED light source was produced and evaluated. The surface free energy is 37.7 mJ/m ² and the hardness is 0.83 GPa. In addition, the width of the convex portion of the replica A-9 produced by the same method as in Example 1 was 415 nm, and the width of the convex portion of the replica B-9 was 69 nm. Furthermore, the same method as the above-mentioned "evaluation of repetitive usability as a replica in a different material" was used to evaluate the reusability. In either of the copy mold A-9 and the copy mold B-9, on the surface of the copy mold after the first use, adhesion of the residue of the second photocurable composition was not observed in SEM observation. However, cracks occurred in the wire, and after 10 times of use, the wire was broken in many places. Furthermore, the repeatability was evaluated by the same method as the above-mentioned "Evaluation of Repeatability as a Copy Model in the Same Material". After using either copy mold A-9 or copy mold B-9, no residue adhesion of the photocurable composition (9) was observed, but the thread was cracked. After 10 times of use, the thread Fractured at multiple locations.

[Comparative Example 3] Preparation of photocurable composition (10), etc. The photocurable composition (1) described in Preparation Example 1 does not contain X-22-2000 as an additive (Shin-Etsu Silicone (silicone) ) The composition made by the company) was then filtered in the same manner as in Example 1. In this way, the photocurable composition (10) was prepared. Using the obtained photocurable composition (10), according to Evaluation Method 1 and Evaluation Method 2, a resin film cured with an LED light source was produced and evaluated. The surface free energy is 41.3 mJ/m ² and the hardness is 0.27 GPa. In addition, the width of the convex portion of the replica A-10 produced by the same method as in Example 1 was 425 nm, and the width of the convex portion of the replica B-10 was 71 nm. Furthermore, the same method as the above-mentioned "evaluation of repetitive usability as a replica in a different material" was used to evaluate the reusability. After using either copy mold A-10 and copy mold B-10 three times, the residue of the second photocurable composition adhered visually. In addition, the result of SEM observation was that the residue of the second photocurable composition adhered between the buried wire and the wire. Furthermore, the repeatability was evaluated by the same method as the above-mentioned "Evaluation of Repeatability as a Copy Model in the Same Material". After the copy mold A-10 or the copy mold B-10 was brought into contact with the photocurable composition (10) and cured by UV irradiation, peeling was attempted, but it adhered strongly and could not be peeled. That is, it cannot be used repeatedly in the same material.

The composition information (blended components), surface free energy and hardness of the photocurable composition, evaluation results of reusability as a replica mold, etc. are summarized in Table 1 and Table 2.

[Table 1] Table 1 Composition of light-curable composition Physical property value of resin after light curing Surface free energy hardness Example Light-curable composition Light-curing monomer (A) Adhesive resin (B) Additive (C) Light hardening initiator (D) Other additives mJ/m ² GPa Example 1 (1) The mass ratio of bis(3-ethyl-3-oxetanylmethyl) ether to 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate is 7/3 mixture no X-22-2000 CPI-310B no 26.2 0.28 Example 2 (2) The mass ratio of bis(3-ethyl-3-oxetanylmethyl) ether to 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate is 7/3 mixture no Polymer (C-1) CPI-310B no 32.0 0.22 Example 3 (3) The mass ratio of bis(3-ethyl-3-oxetanylmethyl) ether to 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate is 7/3 mixture no X-22-2000/Polymer (C-1) CPI-310B no 36.8 0.25 Example 4 (4) Limonene Dioxide no BY16-876/polymer (C-1) CPI-310B Anthracure UVS-1331 (sensitizer) 33.2 0.24 Example 5 (5) The mass ratio of bis(3-ethyl-3-oxetanylmethyl) ether to 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate is 7/3 Adhesive resin (B-1) X-22-2000 CPI-310B no 34.2 0.23 Example 6 (6) The mass ratio of bis(3-ethyl-3-oxetanylmethyl) ether to 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate is 7/3 mixture no Polymer (C-2) CPI-310B no 28.5 0.25 Example 7 (7) The mass ratio of bis(3-ethyl-3-oxetanylmethyl) ether to 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate is 7/3 mixture no FM-DA11/Polymer (C-1) CPI-310B no 25.7 0.27 Comparative example 1 (8) Methyl methacrylate no no Irgacure 184 no 42.7 0.35 Comparative example 2 (9) The mass ratio of pentaerythritol triacrylate/acrylate polymer 4/1 no no Irgacure 184 Methyl acetate and MEK 37.7 0.83 Comparative example 3 (10) The mass ratio of bis(3-ethyl-3-oxetanylmethyl) ether to 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate is 7/3 mixture no no CPI-310B no 41.3 0.27

[Table 2] Table 2 Evaluation after repeated use 50 times Copy mode A Copy mode B Example Light-curable composition Line width (nm) <> indicates the size of the copy mold. Upper section: non-identical materials Lower section: same materials determination Line width (nm) <> indicates the size of the copy mold. Upper section: non-identical materials Lower section: same materials determination Example 1 (1) 449 ＜449＞ ○ 74 ＜74＞ ○ 449 ＜449＞ ○ 74 ＜74＞ ○ Example 2 (2) 449 ＜449＞ ○ 73 ＜73＞ ○ 449 ＜449＞ ○ 73 ＜73＞ ○ Example 3 (3) 448 ＜448＞ ○ 75 ＜75＞ ○ 448 ＜448＞ ○ 75 ＜75＞ ○ Example 4 (4) 448 ＜448＞ ○ 74 ＜74＞ ○ 448 ＜448＞ ○ 74 ＜74＞ ○ Example 5 (5) 450 ＜450＞ ○ 74 ＜74＞ ○ 450 ＜450＞ ○ 74 ＜74＞ ○ Example 6 (6) 448 ＜448＞ ○ 74 ＜74＞ ○ 448 ＜448＞ ○ 74 ＜74＞ ○ Example 7 (7) 448 ＜448＞ ○ 74 ＜74＞ ○ 448 ＜448＞ ○ 74 ＜74＞ ○ Comparative example 1 (8) Unable to measure (resin adheres after 1 use) X Unable to measure (resin adheres after 1 use) X Unable to measure (dissolve after 1 use) X Unable to measure (dissolve after 1 use) X Comparative example 2 (9) The thread breaks after 10 times of use (the sound part is 415 nm/<415 nm>) X The thread breaks after 10 times of use (the sound part is 69 nm/<69 nm>) X The thread breaks after 10 times of use (the sound part is 415 nm/<415 nm>) X The thread breaks after 10 times of use (the sound part is 415 nm/<415 nm>) X Comparative example 3 (10) Unable to measure (resin adheres after 3 times of use) X Unable to measure (resin adheres after 3 times of use) X Unable to measure (closely connected after 1 use) X Unable to measure (closely connected after 1 use) X

In the "Judgment" column of Table 2, regarding the results of the SEM observation of the replica after use, the shape of the concave-convex structure of the replica A and replica B will not change after 50 times of use, and the line width will not be the same as when the replica was made. The case of change is expressed as ○ (good), and the case of resin adhesion (unmeasurable) or fracture is expressed as × (poor).

According to the above, the replica mold made from the photocurable composition of Example 1 has good repeatability. That is, when it was used at least 50 times, no residue of the second photocurable composition was observed to adhere to the surface. In addition, it was possible to maintain a state in which deterioration of the replica mold such as thread breakage was suppressed, and it was possible to reuse it.

This application claims priority based on Japanese Application No. 2019-129863 filed on July 12, 2019, and incorporates all the contents disclosed in this application.

no

Figure 1 is the use of time-of-flight secondary ion mass spectroscopy (Time of Flight Secondary Ion Mass Spectroscopy, TOF-SIMS) of the photocurable composition (1) described in Example 1 of the replica model B-1 The result of mapping the profile.

Claims (9)

A photocurable composition for forming the resin layer of a concavo-convex structure including a substrate and a resin layer, the resin layer is provided on the substrate and has fine concavities and convexities formed on the surface, and the photocurable composition Among them, the surface free energy measured by the following evaluation method 1 is 15 mJ/m ² to 40 mJ/m ² , and the hardness measured by the following evaluation method 2 is 0.05 GPa to 0.5 GPa; (evaluation method 1) First, the photocurable composition is applied to the substrate to form a photocurable film, and ultraviolet rays are irradiated to obtain a cured cured film; secondly, the relative values of water, diiodomethane, and 1-bromonaphthalene are measured using a contact angle meter. The contact angle of the cured film; Then, calculate the surface free energy according to Kitazaki-Hata's theory; (Evaluation method 2) First, use the same method as the evaluation method 1 to obtain the cured film; Second, use nanoindentation The instrument presses the Bosch indenter against the cured film, and calculates the hardness based on the value of the detected stress. The photocurable composition according to claim 1, wherein The photocurable composition includes (a) a photocurable monomer, or a photocurable monomer and a binder resin, and (b) an additive having a photoreactive functional group, With respect to the total amount of the (a) photocurable monomer, or the photocurable monomer and the binder resin, and the (b) additive having a photoreactive functional group, the (b) has photoreactivity The content rate of the functional group additive is 0.001% by mass to 10% by mass. The photocurable composition according to claim 2, wherein the (b) additive having a photoreactive functional group contains the additive represented by the following general formula (1) and/or contains the additive represented by the following general formula (2) ) Additives of the indicated structure;

In the general formula (1), R _{1 is the} same or different and represents selected from a hydrogen atom, a fluorine atom, a halogen atom, a hydrocarbon group having 1 to 20 carbons, an aryl group having 6 to 20 carbons, and an alkane having 6 to 20 carbons. Group, any atom or group in the group consisting of a polyether group with 1 to 20 carbons and a fluorocarbon group with 1 to 20 carbons _{, at least one of L 1} contains an epoxy group, a hydroxyl group, and an amino group , Vinyl ether group, lactone group, propenyl ether group, alkene group, oxetanyl group, vinyl group, acrylate group, methanol group and carboxyl group consisting of photoreactive functional group, in L ₁ is not the case where the photoreactive functional group, the same or different, represent R ₁ is selected from the atom or group, n and 1-n represents the ratio of the units;

In the general formula (2), L ₂ is selected from epoxy groups, amino groups, vinyl ether groups, lactone groups, propenyl ether groups, alcohol groups, alkene groups, oxetanyl groups, vinyl groups, and acrylate groups. At least one of R ₂ to R ₅ is selected from the group consisting of fluorine, fluorine-containing alkyl group having 1 to 10 carbon atoms, and fluorine-containing carbon number A fluorine-containing group in the group consisting of 1-10 alkoxy groups and fluorine-containing alkoxyalkyl groups having 2-10 carbon atoms. When R ₂ to R _{5 are} not fluorine-containing groups, R ₂ to R ₅ are organic groups selected from the group consisting of hydrogen, alkyl groups having 1 to 10 carbons, alkoxy groups having 1 to 10 carbons, and alkoxyalkyl groups having 2 to 10 carbons, R ₂ to R ₅ may be the same or different. In addition, R ₂ to R ₅ may be bonded to each other to form a ring structure. The dotted line indicates that the bond of the part may be a carbon-carbon single bond or a carbon-carbon double bond. The photocurable composition according to any one of claims 1 to 3, which contains a photocuring initiator. The photocurable composition according to Claim 2 or Claim 3, wherein The photocurable monomer includes a compound having a ring-opening polymerizable group capable of undergoing cationic polymerization. A method for manufacturing a concavo-convex structure, which uses the photocurable composition according to any one of claims 1 to 3 to manufacture a concavo-convex structure, the concavo-convex structure comprising: a substrate; and a resin layer, Is provided on the substrate with fine concavities and convexities formed on the surface, and the manufacturing method of the concavo-convex structure includes a crimping step, The crimping step is to crimp a mold with a fine concave-convex pattern to the photo-curable layer provided on the substrate by the photo-curable composition, thereby forming and contacting the surface of the resin layer. The fine concavo-convex pattern corresponding to the fine concavo-convex pattern. The manufacturing method of the concavo-convex structure according to claim 6, which further includes: A light irradiating step, after the crimping step, irradiating light in a state where the mold is crimped to thereby harden the photocurable layer to form a hardened layer; and In the peeling step, the mold is peeled from the hardened layer. A method of forming a fine concavo-convex pattern, which is to repeatedly use a substrate comprising a resin layer to form the fine concavo-convex pattern, the resin layer being composed of the photocurable composition according to any one of claims 1 to 3 The surface is formed with fine concavities and convexities. A concave-convex structure body, including: Substrate; and The resin layer is provided on the substrate and is formed of the photocurable composition according to any one of claims 1 to 3, and has fine irregularities formed on the surface.

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